JP5742218B2 - Polymerizable composition, resin molded body, and laminate - Google Patents
Polymerizable composition, resin molded body, and laminate Download PDFInfo
- Publication number
- JP5742218B2 JP5742218B2 JP2010294332A JP2010294332A JP5742218B2 JP 5742218 B2 JP5742218 B2 JP 5742218B2 JP 2010294332 A JP2010294332 A JP 2010294332A JP 2010294332 A JP2010294332 A JP 2010294332A JP 5742218 B2 JP5742218 B2 JP 5742218B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- polymerizable composition
- resin molded
- laminate
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011347 resin Substances 0.000 title claims description 100
- 229920005989 resin Polymers 0.000 title claims description 100
- 239000000203 mixture Substances 0.000 title claims description 83
- 150000001875 compounds Chemical class 0.000 claims description 137
- -1 methacrylate compound Chemical class 0.000 claims description 65
- 239000000178 monomer Substances 0.000 claims description 56
- 230000001588 bifunctional effect Effects 0.000 claims description 46
- 150000001925 cycloalkenes Chemical class 0.000 claims description 38
- 238000004132 cross linking Methods 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 24
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 23
- 239000000945 filler Substances 0.000 claims description 20
- 238000012662 bulk polymerization Methods 0.000 claims description 19
- 239000003431 cross linking reagent Substances 0.000 claims description 17
- 239000002685 polymerization catalyst Substances 0.000 claims description 17
- 239000012986 chain transfer agent Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 description 35
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 30
- 238000007747 plating Methods 0.000 description 29
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 22
- 239000003063 flame retardant Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 239000000835 fiber Substances 0.000 description 17
- 229910052707 ruthenium Inorganic materials 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 15
- 125000004429 atom Chemical group 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 239000010410 layer Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000003712 anti-aging effect Effects 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000005649 metathesis reaction Methods 0.000 description 12
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 239000012779 reinforcing material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 125000002723 alicyclic group Chemical group 0.000 description 8
- 238000013329 compounding Methods 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000001723 curing Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 125000005641 methacryl group Chemical group 0.000 description 6
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 6
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 4
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical group CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 3
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 3
- LURVUWBWEGPODG-UHFFFAOYSA-L dichlororuthenium;tricyclohexylphosphane Chemical compound [Cl-].[Cl-].[Ru+2].C1CCCCC1P(C1CCCCC1)C1CCCCC1 LURVUWBWEGPODG-UHFFFAOYSA-L 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229910052762 osmium Inorganic materials 0.000 description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- 150000003003 phosphines Chemical class 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 150000003624 transition metals Chemical group 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical compound CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 2
- QEGNUYASOUJEHD-UHFFFAOYSA-N 1,1-dimethylcyclohexane Chemical compound CC1(C)CCCCC1 QEGNUYASOUJEHD-UHFFFAOYSA-N 0.000 description 2
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- MZVABYGYVXBZDP-UHFFFAOYSA-N 1-adamantyl 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)C(=C)C)C3 MZVABYGYVXBZDP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- JMIZWXDKTUGEES-UHFFFAOYSA-N 2,2-di(cyclopenten-1-yloxy)ethyl 2-methylprop-2-enoate Chemical compound C=1CCCC=1OC(COC(=O)C(=C)C)OC1=CCCC1 JMIZWXDKTUGEES-UHFFFAOYSA-N 0.000 description 2
- ZDTLUUIYCAMIMQ-UHFFFAOYSA-N 2-(2-hydroxyethoxy)-1-methoxyethanol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.COC(O)COCCO ZDTLUUIYCAMIMQ-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 2
- FSWCCQWDVGZMRD-UHFFFAOYSA-N 4-methylcyclohexene Chemical compound CC1CCC=CC1 FSWCCQWDVGZMRD-UHFFFAOYSA-N 0.000 description 2
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- QQVPOWKGJPEUJJ-UHFFFAOYSA-N C(C(=C)C)(=O)OC=CCCCCCC.C(C(=C)C)(=O)OCCOC1=CC=CC=C1 Chemical compound C(C(=C)C)(=O)OC=CCCCCCC.C(C(=C)C)(=O)OCCOC1=CC=CC=C1 QQVPOWKGJPEUJJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- PLUDEAUQZKPAIN-UHFFFAOYSA-N bis(4-methylphenyl) hydrogen phosphate Chemical compound C1=CC(C)=CC=C1OP(O)(=O)OC1=CC=C(C)C=C1 PLUDEAUQZKPAIN-UHFFFAOYSA-N 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000007766 curtain coating Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
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- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- LLXZODPVPXJXPD-UHFFFAOYSA-N n,n-dimethylbicyclo[2.2.1]hept-2-en-5-amine Chemical compound C1C2C(N(C)C)CC1C=C2 LLXZODPVPXJXPD-UHFFFAOYSA-N 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- PZUGJLOCXUNFLM-UHFFFAOYSA-N n-ethenylaniline Chemical group C=CNC1=CC=CC=C1 PZUGJLOCXUNFLM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical group C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- KOPQZJAYZFAPBC-UHFFFAOYSA-N propanoyl propaneperoxoate Chemical compound CCC(=O)OOC(=O)CC KOPQZJAYZFAPBC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- XTXFUQOLBKQKJU-UHFFFAOYSA-N tert-butylperoxy(trimethyl)silane Chemical compound CC(C)(C)OO[Si](C)(C)C XTXFUQOLBKQKJU-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical group C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- UAIFZYSPVVBOPN-UHFFFAOYSA-N trimethyl(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(C)C UAIFZYSPVVBOPN-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- SUDSHRFJYWYREN-UHFFFAOYSA-N tris(ethenyl)-prop-2-enylsilane Chemical compound C=CC[Si](C=C)(C=C)C=C SUDSHRFJYWYREN-UHFFFAOYSA-N 0.000 description 1
- GNFABDZKXNKQKN-UHFFFAOYSA-N tris(prop-2-enyl)phosphane Chemical compound C=CCP(CC=C)CC=C GNFABDZKXNKQKN-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Description
本発明は、重合性組成物、樹脂成形体、及び積層体に関する。詳しくは、高周波領域での誘電正接が極めて小さく、配線埋め込み性、耐熱性、及びめっき性に優れた積層体の製造に有用な、重合性組成物、架橋性樹脂成形体及び架橋樹脂成形体、並びに、それらを用いて得られる積層体に関する。 The present invention relates to a polymerizable composition, a resin molded body, and a laminate. Specifically, the polymerizable composition, the crosslinkable resin molded body, and the crosslinked resin molded body, which have a very small dielectric loss tangent in a high frequency region and are useful for producing a laminate excellent in wiring embedding property, heat resistance, and plating property, In addition, the present invention relates to a laminate obtained by using them.
近年、高度情報化時代を迎え、情報伝送は高速化・高周波化に動き出し、マイクロ波通信やミリ波通信が現実になってきている。これらの高周波化時代の回路基板には、高周波における伝送ロスを極限まで軽減するために誘電正接が小さい材料が求められている。誘電正接が小さい樹脂材料としてはシクロオレフィンモノマーを重合したシクロオレフィンポリマーが注目されている。 In recent years, with the advent of advanced information technology, information transmission has begun to increase in speed and frequency, and microwave communication and millimeter wave communication have become a reality. For these circuit boards in the high frequency era, a material having a low dielectric loss tangent is required in order to reduce transmission loss at high frequencies to the limit. As a resin material having a small dielectric loss tangent, a cycloolefin polymer obtained by polymerizing a cycloolefin monomer has attracted attention.
かかるシクロオレフィンポリマーを用いた基板材料としては、これまでに種々のものが知られているが、例えば、特許文献1には、高周波領域での誘電正接が極めて小さく、配線埋め込み性、耐熱性、及び冷熱衝撃試験での耐クラック性に優れた積層体の製造に有用な、シクロオレフィンモノマー、重合触媒、架橋剤、及び反応性流動化剤を含有してなる重合性組成物、並びにそれを用いてなる、架橋性樹脂成形体(例えば、プリプレグ)、架橋樹脂成形体、及び積層体が開示されている。反応性流動化剤としては、重合性の炭素−炭素不飽和結合を持たず、かつ架橋性の炭素−炭素不飽和結合を1つ有する単官能化合物が用いられることが、また、前記積層体は高周波基板材料として有用であることが、記載されている。 As a substrate material using such a cycloolefin polymer, various materials have been known so far. For example, in Patent Document 1, a dielectric loss tangent in a high frequency region is extremely small, wiring embedding property, heat resistance, And a polymerizable composition containing a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a reactive fluidizing agent, which are useful for producing a laminate having excellent crack resistance in a thermal shock test, and using the same A crosslinkable resin molded body (for example, prepreg), a crosslinked resin molded body, and a laminate are disclosed. As the reactive fluidizing agent, a monofunctional compound that does not have a polymerizable carbon-carbon unsaturated bond and has one crosslinkable carbon-carbon unsaturated bond is used. It is described that it is useful as a high-frequency substrate material.
本発明者らは、前記特許文献1に従ってプリプレグ及び積層体を得、それらの特性について調べたところ、当該プリプレグによれば前記の通りの特性を有する積層体が得られるが、めっき性に劣る場合があることが明らかになった。
本発明の目的は、高周波領域での誘電正接が極めて小さく、配線埋め込み性、耐熱性、及びめっき性に優れた積層体の製造に有用な、重合性組成物、架橋性樹脂成形体及び架橋樹脂成形体、並びに、それらを用いて得られる積層体を提供することにある。
The present inventors obtained a prepreg and a laminate according to Patent Document 1 and investigated their properties. According to the prepreg, a laminate having the above-described properties can be obtained, but the plating property is poor. It became clear that there is.
An object of the present invention is to provide a polymerizable composition, a crosslinkable resin molded article, and a crosslinkable resin, which have a very small dielectric loss tangent in a high frequency region and are useful for producing a laminate excellent in wiring embedding property, heat resistance, and plating property. It is providing the molded object and the laminated body obtained by using them.
本発明者らは、上記課題に鑑み鋭意検討の結果、シクロオレフィンモノマー、重合触媒、架橋剤、並びに架橋助剤として所定の割合で一官能、二官能、及び三官能のメタクリレート化合物を含む重合性組成物によれば、加熱硬化時の樹脂流動性に優れたプリプレグが得られ、当該プリプレグによれば、高周波領域での誘電正接が極めて小さく、配線埋め込み性、耐熱性、及びめっき性に優れた積層体が得られることを見出した。本発明者らは、かかる知見に基づき本発明を完成させるに至った。 As a result of intensive studies in view of the above-mentioned problems, the present inventors have obtained a polymerizable compound containing a monofunctional, bifunctional, and trifunctional methacrylate compound at a predetermined ratio as a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, and a crosslinking aid. According to the composition, a prepreg excellent in resin fluidity at the time of heat curing is obtained. According to the prepreg, the dielectric loss tangent in the high frequency region is extremely small, and the wiring embedding property, heat resistance, and plating property are excellent. It has been found that a laminate can be obtained. Based on this knowledge, the inventors have completed the present invention.
すなわち、本発明によれば、
〔1〕シクロオレフィンモノマー、重合触媒、架橋剤、ビニリデン基を1つ有する一官能化合物、ビニリデン基を2つ有する二官能化合物、及びビニリデン基を3つ有する三官能化合物を含有してなり、かつ前記一官能化合物、前記二官能化合物、及び前記三官能化合物の含有割合が重量比(一官能化合物:二官能化合物:三官能化合物)で1〜20:0.1〜20:10〜25である、重合性組成物、
〔2〕一官能化合物が一官能メタクリレート化合物であり、二官能化合物が二官能メタクリレート化合物であり、三官能化合物が三官能メタクリレート化合物である、前記〔1〕記載の重合性組成物、
〔3〕充填剤をさらに含有する前記〔1〕又は〔2〕記載の重合性組成物、
〔4〕連鎖移動剤をさらに含有する前記〔1〕〜〔3〕いずれか記載の重合性組成物、
〔5〕前記〔1〕〜〔4〕のいずれかに記載の重合性組成物を塊状重合してなる架橋性樹脂成形体、
〔6〕前記〔1〕〜〔4〕のいずれかに記載の重合性組成物を塊状重合してなる重合体を架橋してなる架橋樹脂成形体、並びに
〔7〕少なくとも、前記〔5〕に記載の架橋性樹脂成形体、又は前記〔6〕に記載の架橋樹脂成形体からなる層を有してなる積層体、
が提供される。
That is, according to the present invention,
[1] a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a monofunctional compound having one vinylidene group, a bifunctional compound having two vinylidene groups, and a trifunctional compound having three vinylidene groups, and The content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is 1 to 20: 0.1 to 20:10 to 25 by weight ratio (monofunctional compound: bifunctional compound: trifunctional compound). , Polymerizable compositions,
[2] The polymerizable composition according to [1], wherein the monofunctional compound is a monofunctional methacrylate compound, the bifunctional compound is a bifunctional methacrylate compound, and the trifunctional compound is a trifunctional methacrylate compound,
[3] The polymerizable composition according to [1] or [2], further containing a filler,
[4] The polymerizable composition according to any one of [1] to [3], further containing a chain transfer agent,
[5] A crosslinkable resin molded article obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [4],
[6] A crosslinked resin molded product obtained by crosslinking a polymer obtained by bulk polymerization of the polymerizable composition according to any one of [1] to [4], and [7] at least in the above [5]. Or a laminate comprising a layer made of the crosslinked resin molded article according to [6],
Is provided.
本発明によれば、高周波領域での誘電正接が極めて小さく、配線埋め込み性、耐熱性、及びめっき性に優れた積層体の製造に有用な、重合性組成物、架橋性樹脂成形体及び架橋樹脂成形体、並びに前記特性を有する積層体を提供することができる。本発明の積層体は、通信機器用途等に用いられるマイクロ波又はミリ波等の高周波回路基板の製造に好適に使用することができる。 According to the present invention, a polymerizable composition, a crosslinkable resin molded article, and a crosslinkable resin, which have a very low dielectric loss tangent in a high frequency region and are useful for producing a laminate excellent in wiring embedding property, heat resistance, and plating property. A molded body and a laminate having the above-described properties can be provided. The laminate of the present invention can be suitably used for the production of high-frequency circuit boards such as microwaves or millimeter waves used for communication equipment applications.
本発明の重合性組成物は、シクロオレフィンモノマー、重合触媒、架橋剤、ビニリデン基を1つ有する一官能化合物、ビニリデン基を2つ有する二官能化合物、及びビニリデン基を3つ有する三官能化合物を含有してなり、かつ前記一官能化合物、前記二官能化合物、及び前記三官能化合物の含有割合が重量比(一官能化合物:二官能化合物:三官能化合物)で1〜20:0.1〜20:10〜25であるものである。 The polymerizable composition of the present invention comprises a cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a monofunctional compound having one vinylidene group, a bifunctional compound having two vinylidene groups, and a trifunctional compound having three vinylidene groups. The content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is 1 to 20: 0.1 to 20 in a weight ratio (monofunctional compound: bifunctional compound: trifunctional compound). : 10-25.
(シクロオレフィンモノマー)
本発明に使用されるシクロオレフィンモノマーは、炭素原子で形成される脂環構造を有し、かつ該脂環構造中に重合性の炭素−炭素二重結合を1つ有する化合物である。本明細書において「重合性の炭素−炭素二重結合」とは、連鎖重合(開環重合)可能な炭素−炭素二重結合をいう。開環重合には、イオン重合、ラジカル重合、及びメタセシス重合など、種々の形態のものが存在するが、本発明においては、通常、メタセシス開環重合をいう。
(Cycloolefin monomer)
The cycloolefin monomer used in the present invention is a compound having an alicyclic structure formed of carbon atoms and having one polymerizable carbon-carbon double bond in the alicyclic structure. As used herein, “polymerizable carbon-carbon double bond” refers to a carbon-carbon double bond capable of chain polymerization (ring-opening polymerization). There are various types of ring-opening polymerization, such as ionic polymerization, radical polymerization, and metathesis polymerization. In the present invention, it generally refers to metathesis ring-opening polymerization.
シクロオレフィンモノマーの脂環構造としては、単環、多環、縮合多環、橋かけ環及びこれらの組み合わせ多環などが挙げられる。各脂環構造を構成する炭素数に特に限定はないが、通常、4〜30個、好ましくは5〜20個、より好ましくは5〜15個である。
シクロオレフィンモノマーは、アルキル基、アルケニル基、アルキリデン基、及びアリール基などの、炭素数1〜30の炭化水素基や、カルボキシル基や酸無水物基などの極性基を置換基として有していてもよいが、得られる積層体を低誘電正接とする観点から、極性基を持たない、すなわち、炭素原子と水素原子のみで構成されるものが好ましい。
Examples of the alicyclic structure of the cycloolefin monomer include monocycles, polycycles, condensed polycycles, bridged rings, and combination polycycles thereof. Although there is no limitation in particular in carbon number which comprises each alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces.
The cycloolefin monomer has a hydrocarbon group having 1 to 30 carbon atoms such as an alkyl group, an alkenyl group, an alkylidene group, and an aryl group, and a polar group such as a carboxyl group or an acid anhydride group as a substituent. However, from the viewpoint of making the obtained laminate a low dielectric loss tangent, those having no polar group, that is, comprising only carbon atoms and hydrogen atoms are preferable.
シクロオレフィンモノマーとしては、単環のシクロオレフィンモノマーと多環のシクロオレフィンモノマーのいずれをも用いることができる。得られる積層体の誘電特性、及び耐熱性の特性を高度にバランスさせる観点から、多環のシクロオレフィンモノマーが好ましい。多環のシクロオレフィンモノマーとしては、特にノルボルネン系モノマーが好ましい。「ノルボルネン系モノマー」とは、ノルボルネン環構造を分子内に有するシクロオレフィンモノマーをいう。例えば、ノルボルネン類、ジシクロペンタジエン類、及びテトラシクロドデセン類などが挙げられる。 As the cycloolefin monomer, either a monocyclic cycloolefin monomer or a polycyclic cycloolefin monomer can be used. From the viewpoint of highly balancing the dielectric properties and heat resistance properties of the resulting laminate, polycyclic cycloolefin monomers are preferred. As the polycyclic cycloolefin monomer, a norbornene-based monomer is particularly preferable. The “norbornene monomer” refers to a cycloolefin monomer having a norbornene ring structure in the molecule. Examples include norbornenes, dicyclopentadiene, and tetracyclododecene.
シクロオレフィンモノマーとしては、架橋性の炭素−炭素不飽和結合を持たないものと、架橋性の炭素−炭素不飽和結合を1以上有するもののいずれをも用いることができる。本明細書において「架橋性の炭素−炭素不飽和結合」とは、開環重合には関与せず、架橋反応に関与可能な炭素−炭素不飽和結合をいう。架橋反応とは橋架け構造を形成する反応であり、縮合反応、付加反応、ラジカル反応、及びメタセシス反応など、種々の形態のものが存在するが、本発明においては、通常、ラジカル架橋反応又はメタセシス架橋反応、特にラジカル架橋反応をいう。架橋性の炭素−炭素不飽和結合としては、芳香族炭素−炭素不飽和結合を除く炭素−炭素不飽和結合、すなわち、脂肪族炭素−炭素二重結合又は三重結合が挙げられ、本発明においては、通常、脂肪族炭素−炭素二重結合をいう。架橋性の炭素−炭素不飽和結合を1以上有するシクロオレフィンモノマー中、不飽和結合の位置は特に限定されるものではなく、炭素原子で形成される脂環構造内の他、該脂環構造以外の任意の位置、例えば、側鎖の末端や内部に存在していてもよい。例えば、前記脂肪族炭素−炭素二重結合は、ビニル基(CH2=CH−)、ビニリデン基(CH2=C<)、又はビニレン基(−CH=CH−)として存在し得、良好にラジカル架橋反応性を発揮することから、ビニル基及び/又はビニリデン基として存在するのが好ましく、ビニリデン基として存在するのがより好ましい。 As the cycloolefin monomer, any of those having no crosslinkable carbon-carbon unsaturated bond and those having one or more crosslinkable carbon-carbon unsaturated bonds can be used. As used herein, “crosslinkable carbon-carbon unsaturated bond” refers to a carbon-carbon unsaturated bond that does not participate in ring-opening polymerization and can participate in a crosslinking reaction. The cross-linking reaction is a reaction that forms a bridge structure, and there are various forms such as a condensation reaction, an addition reaction, a radical reaction, and a metathesis reaction. It refers to a crosslinking reaction, particularly a radical crosslinking reaction. Examples of the crosslinkable carbon-carbon unsaturated bond include carbon-carbon unsaturated bonds other than aromatic carbon-carbon unsaturated bonds, that is, aliphatic carbon-carbon double bonds or triple bonds. Usually refers to an aliphatic carbon-carbon double bond. In the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds, the position of the unsaturated bond is not particularly limited, and in addition to the alicyclic structure formed by carbon atoms, other than the alicyclic structure It may be present at any position of, for example, at the end or inside of the side chain. For example, the aliphatic carbon-carbon double bond may exist as a vinyl group (CH 2 ═CH—), a vinylidene group (CH 2 ═C <), or a vinylene group (—CH═CH—). Since it exhibits radical crosslinking reactivity, it is preferably present as a vinyl group and / or vinylidene group, and more preferably as a vinylidene group.
架橋性の炭素−炭素不飽和結合を持たないシクロオレフィンモノマーとしては、例えば、シクロペンテン、3−メチルシクロペンテン、4−メチルシクロペンテン、3,4−ジメチルシクロペンテン、3,5−ジメチルシクロペンテン、3−クロロシクロペンテン、シクロへキセン、3−メチルシクロへキセン、4−メチルシクロヘキセン、3,4−ジメチルシクロヘキセン、3−クロロシクロヘキセン、及びシクロへプテンなどの単環シクロオレフィンモノマー;ノルボルネン、5−メチル−2−ノルボルネン、5−エチル−2−ノルボルネン、5−プロピル−2−ノルボルネン、5,6−ジメチル−2−ノルボルネン、1−メチル−2−ノルボルネン、7−メチル−2−ノルボルネン、5,5,6−トリメチル−2−ノルボルネン、5−フェニル−2−ノルボルネン、テトラシクロドデセン、1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン(TCD)、2−メチル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2−エチル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2,3−ジメチル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2−ヘキシル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2−エチリデン−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2−フルオロ−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、1,5−ジメチル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2−シクロへキシル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2,3−ジクロロ−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、2−イソブチル−1,4,5,8−ジメタノ−1,2,3,4,4a,5,8,8a−オクタヒドロナフタレン、1,2−ジヒドロジシクロペンタジエン、5−クロロ−2−ノルボルネン、5,5−ジクロロ−2−ノルボルネン、5−フルオロ−2−ノルボルネン、5,5,6−トリフルオロ−6−トリフルオロメチル−2−ノルボルネン、5−クロロメチル−2−ノルボルネン、5−メトキシ−2−ノルボルネン、5,6−ジカルボキシル−2−ノルボルネンアンハイドレート、5−ジメチルアミノ−2−ノルボルネン、及び5−シアノ−2−ノルボルネンなどのノルボルネン系モノマー;を挙げることができ、好ましくは架橋性の炭素−炭素不飽和結合を持たないノルボルネン系モノマーである。 Examples of cycloolefin monomers having no crosslinkable carbon-carbon unsaturated bond include cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, and 3-chlorocyclopentene. Monocyclic cycloolefin monomers such as cyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, and cycloheptene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-propyl-2-norbornene, 5,6-dimethyl-2-norbornene, 1-methyl-2-norbornene, 7-methyl-2-norbornene, 5,5,6-trimethyl- 2-norbornene, 5- Enyl-2-norbornene, tetracyclododecene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (TCD), 2-methyl-1, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4 4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2- Hexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1, , 5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4 , 4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2, , 3-Dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1 , 2,3,4,4a, 5,8,8a-octahydronaphthalene, 1,2-dihydrodicyclopentadiene, 5-chloro-2-norbornene, 5,5-dichloro-2-norbornene, 5-fluoro- 2-norbornene, 5,5,6-trifluoro-6-tri Fluoromethyl-2-norbornene, 5-chloromethyl-2-norbornene, 5-methoxy-2-norbornene, 5,6-dicarboxyl-2-norbornene anhydrate, 5-dimethylamino-2-norbornene, and 5- Norbornene monomers such as cyano-2-norbornene; and norbornene monomers having no crosslinkable carbon-carbon unsaturated bond are preferable.
架橋性の炭素−炭素不飽和結合を1以上有するシクロオレフィンモノマーとしては、例えば、3−ビニルシクロヘキセン、4−ビニルシクロヘキセン、1,3−シクロペンタジエン、1,3−シクロへキサジエン、1,4−シクロへキサジエン、5−エチル−1,3−シクロへキサジエン、1,3−シクロへプタジエン、及び1,3−シクロオクタジエンなどの単環シクロオレフィンモノマー;5−エチリデン−2−ノルボルネン、5−メチリデン−2−ノルボルネン、5−イソプロピリデン−2−ノルボルネン、5−ビニル−2−ノルボルネン、5−アリル−2−ノルボルネン、5,6−ジエチリデン−2−ノルボルネン、ジシクロペンタジエン、エチリデンテトラシクロ[6.2.1.13,6.02,7]ドデカ−4−エン及び2,5−ノルボルナジエンなどのノルボルネン系モノマー;を挙げることができ、好ましくは架橋性の炭素−炭素不飽和結合を1以上有するノルボルネン系モノマーである。
これらのシクロオレフィンモノマーは、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。
Examples of the cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds include 3-vinylcyclohexene, 4-vinylcyclohexene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4- Monocyclic cycloolefin monomers such as cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, and 1,3-cyclooctadiene; 5-ethylidene-2-norbornene, 5- Methylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 5,6-diethylidene-2-norbornene, dicyclopentadiene, ethylidenetetracyclo [6 2.1.1 3,6 . 0 2,7 ] norbornene monomers such as dodeca-4-ene and 2,5-norbornadiene; preferred are norbornene monomers having one or more crosslinkable carbon-carbon unsaturated bonds.
These cycloolefin monomers can be used alone or in combination of two or more.
本発明に使用されるシクロオレフィンモノマーとしては、架橋性の炭素−炭素不飽和結合を1以上有するシクロオレフィンモノマーを含むものが好ましい。かかるシクロオレフィンモノマーを用いると、得られる積層体の信頼性が向上し、好適である。
本発明の重合性組成物に配合するシクロオレフィンモノマー中、架橋性の炭素−炭素不飽和結合を1以上有するシクロオレフィンモノマーと架橋性の炭素−炭素不飽和結合を持たないシクロオレフィンモノマーとの配合割合は所望により適宜選択すればよいが、重量比の値(架橋性の炭素−炭素不飽和結合を1以上有するシクロオレフィンモノマー/架橋性の炭素−炭素不飽和結合を持たないシクロオレフィンモノマー)で、通常、5/95〜100/0、好ましくは10/90〜90/10、より好ましくは15/85〜70/30の範囲である。当該配合割合がかかる範囲にあれば、得られる積層体において、耐熱性を高度に向上させることができ、好適である。
The cycloolefin monomer used in the present invention preferably includes a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds. When such a cycloolefin monomer is used, the reliability of the obtained laminate is improved, which is preferable.
In the cycloolefin monomer blended in the polymerizable composition of the present invention, a blend of a cycloolefin monomer having one or more crosslinkable carbon-carbon unsaturated bonds and a cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bonds The ratio may be appropriately selected as desired, but the weight ratio value (cycloolefin monomer having at least one crosslinkable carbon-carbon unsaturated bond / cycloolefin monomer having no crosslinkable carbon-carbon unsaturated bond). Usually, it is in the range of 5/95 to 100/0, preferably 10/90 to 90/10, more preferably 15/85 to 70/30. If the said mixture ratio exists in this range, in the laminated body obtained, heat resistance can be improved highly and it is suitable.
なお、本発明の重合性組成物には、本発明の効果の発現が阻害されない限り、以上のシクロオレフィンモノマーと共重合可能な任意のモノマーが含まれていてもよい。 In addition, as long as expression of the effect of this invention is not inhibited, the polymerizable composition of this invention may contain the arbitrary monomers copolymerizable with the above cycloolefin monomer.
(重合触媒)
本発明に使用される重合触媒としては、前記シクロオレフィンモノマーを重合できるものであれば特に限定はないが、本発明の重合性組成物は、後述の架橋性樹脂成形体の製造において、直接塊状重合に供して用いるのが好適であり、通常、メタセシス重合触媒を用いるのが好ましい。
(Polymerization catalyst)
The polymerization catalyst used in the present invention is not particularly limited as long as it can polymerize the cycloolefin monomer, but the polymerizable composition of the present invention is directly agglomerated in the production of a crosslinkable resin molded article described later. It is preferable to use it for polymerization, and it is usually preferable to use a metathesis polymerization catalyst.
メタセシス重合触媒としては、前記シクロオレフィンモノマーをメタセシス開環重合可能である、通常、遷移金属原子を中心原子として、複数のイオン、原子、多原子イオン、及び化合物などが結合してなる錯体が挙げられる。遷移金属原子としては、5族、6族及び8族(長周期型周期表による。以下、同じ。)の原子が使用される。それぞれの族の原子は特に限定されないが、5族の原子としては、例えば、タンタルが挙げられ、6族の原子としては、例えば、モリブデンやタングステンが挙げられ、8族の原子としては、例えば、ルテニウムやオスミウムが挙げられる。遷移金属原子としては、中でも、8族のルテニウムやオスミウムが好ましい。すなわち、本発明に使用されるメタセシス重合触媒としては、ルテニウム又はオスミウムを中心原子とする錯体が好ましく、ルテニウムを中心原子とする錯体がより好ましい。ルテニウムを中心原子とする錯体としては、カルベン化合物がルテニウムに配位してなるルテニウムカルベン錯体が好ましい。ここで、「カルベン化合物」とは、メチレン遊離基を有する化合物の総称であり、(>C:)で表されるような電荷のない2価の炭素原子(カルベン炭素)を持つ化合物をいう。ルテニウムカルベン錯体は、塊状重合時の触媒活性に優れるため、本発明の重合性組成物を塊状重合に供して架橋性樹脂成形体を得る場合、得られる成形体には未反応のモノマーに由来する臭気が少なく、生産性良く良質な成形体が得られる。また、酸素や空気中の水分に対して比較的安定であって、失活しにくいので、大気下でも使用可能である。 Examples of the metathesis polymerization catalyst include a complex formed by bonding a plurality of ions, atoms, polyatomic ions, compounds, etc. with a transition metal atom as a central atom, which is capable of metathesis ring-opening polymerization of the cycloolefin monomer. It is done. As transition metal atoms, atoms of Group 5, Group 6, and Group 8 (according to the long-period periodic table; the same applies hereinafter) are used. Although the atoms of each group are not particularly limited, examples of the Group 5 atom include tantalum, examples of the Group 6 atom include molybdenum and tungsten, and examples of the Group 8 atom include: Examples include ruthenium and osmium. Among them, the group 8 ruthenium or osmium is preferable as the transition metal atom. That is, the metathesis polymerization catalyst used in the present invention is preferably a complex having ruthenium or osmium as a central atom, and more preferably a complex having ruthenium as a central atom. As the complex having ruthenium as a central atom, a ruthenium carbene complex in which a carbene compound is coordinated to ruthenium is preferable. Here, the “carbene compound” is a general term for compounds having a methylene free group, and refers to a compound having an uncharged divalent carbon atom (carbene carbon) as represented by (> C :). Since the ruthenium carbene complex is excellent in catalytic activity during bulk polymerization, when the crosslinkable resin molded body is obtained by subjecting the polymerizable composition of the present invention to bulk polymerization, the resulting molded body is derived from unreacted monomers. A molded article with low odor and good productivity can be obtained. In addition, it is relatively stable to oxygen and moisture in the air and is not easily deactivated, so that it can be used even in the atmosphere.
ルテニウムカルベン錯体の具体例としては、以下の式(1)又は式(2)で表される錯
体が挙げられる。
Specific examples of the ruthenium carbene complex include complexes represented by the following formula (1) or formula (2).
式(1)及び(2)において、R1及びR2はそれぞれ独立して、水素原子;ハロゲン原子;又はハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子若しくは珪素原子を含んでいてもよい、環状又は鎖状の、炭素数1〜20の炭化水素基を表す。X1及びX2はそれぞれ独立して、任意のアニオン性配位子を示す。L1及びL2はそれぞれ独立して、ヘテロ原子含有カルベン化合物又はヘテロ原子含有カルベン化合物以外の中性電子供与性化合物を表す。また、R1とR2は互いに結合して、ヘテロ原子を含んでいてもよい脂肪族環又は芳香族環を形成してもよい。さらに、R1、R2、X1、X2、L1及びL2は、任意の組合せで互いに結合して多座キレート化配位子を形成してもよい。 In the formulas (1) and (2), R 1 and R 2 each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. It represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. X 1 and X 2 each independently represent an arbitrary anionic ligand. L 1 and L 2 each independently represent a hetero atom-containing carbene compound or a neutral electron donating compound other than the hetero atom-containing carbene compound. R 1 and R 2 may be bonded to each other to form an aliphatic ring or an aromatic ring that may contain a hetero atom. Furthermore, R 1 , R 2 , X 1 , X 2 , L 1 and L 2 may be bonded together in any combination to form a multidentate chelating ligand.
ヘテロ原子とは、周期律表15族及び16族の原子を意味し、具体的には、窒素原子(N)、酸素原子(O)、リン原子(P)、硫黄原子(S)、砒素原子(As)、及びセレン原子(Se)などを挙げることができる。これらの中でも、安定なカルベン化合物が得られる観点から、N、O、P、及びSなどが好ましく、Nが特に好ましい。 A heteroatom means an atom of groups 15 and 16 of the periodic table, and specifically, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S), an arsenic atom (As), a selenium atom (Se), etc. can be mentioned. Among these, N, O, P, and S are preferable from the viewpoint of obtaining a stable carbene compound, and N is particularly preferable.
前記ルテニウムカルベン錯体としては、得られる架橋樹脂成形体及び積層体の機械的強度と耐衝撃性とが高度にバランスされ得ることから、ヘテロ原子含有カルベン化合物としてヘテロ環構造を有するカルベン化合物を配位子として少なくとも1つ有するものが好ましい。ヘテロ環構造としては、イミダゾリン環構造又はイミダゾリジン環構造が好ましい。 As the ruthenium carbene complex, the mechanical strength and impact resistance of the resulting crosslinked resin molded product and laminate can be highly balanced, so that a carbene compound having a heterocyclic structure is coordinated as a heteroatom-containing carbene compound. What has at least 1 child is preferable. As the heterocyclic structure, an imidazoline ring structure or an imidazolidine ring structure is preferable.
ヘテロ環構造を有するカルベン化合物としては、以下の式(3)又は式(4)で示される化合物が挙げられる。 Examples of the carbene compound having a heterocyclic structure include compounds represented by the following formula (3) or formula (4).
式(3)及び(4)において、R3〜R6はそれぞれ独立して、水素原子;ハロゲン原子;又はハロゲン原子、酸素原子、窒素原子、硫黄原子、リン原子若しくは珪素原子を含んでいてもよい、環状又は鎖状の、炭素数1〜20個の炭化水素基を表す。また、R3〜R6は任意の組合せで互いに結合して環を形成していてもよい。 In the formulas (3) and (4), R 3 to R 6 each independently include a hydrogen atom; a halogen atom; or a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom. Represents a good cyclic or chain hydrocarbon group having 1 to 20 carbon atoms. R 3 to R 6 may be bonded to each other in any combination to form a ring.
前記式(3)又は式(4)で表される化合物としては、1,3−ジメシチルイミダゾリジン−2−イリデン、1,3−ジ(1−アダマンチル)イミダゾリジン−2−イリデン、1,3−ジシクロヘキシルイミダゾリジン−2−イリデン、1,3−ジメシチルオクタヒドロベンズイミダゾール−2−イリデン、1,3−ジイソプロピル−4−イミダゾリン−2−イリデン、1,3−ジ(1−フェニルエチル)−4−イミダゾリン−2−イリデン、及び1,3−ジメシチル−2,3−ジヒドロベンズイミダゾール−2−イリデンなどが挙
げられる。
Examples of the compound represented by the formula (3) or the formula (4) include 1,3-dimesitylimidazolidin-2-ylidene, 1,3-di (1-adamantyl) imidazolidin-2-ylidene, 1 , 3-dicyclohexylimidazolidine-2-ylidene, 1,3-dimesityloctahydrobenzimidazol-2-ylidene, 1,3-diisopropyl-4-imidazoline-2-ylidene, 1,3-di (1-phenyl) Ethyl) -4-imidazoline-2-ylidene, 1,3-dimesityl-2,3-dihydrobenzimidazol-2-ylidene, and the like.
また、前記式(3)又は式(4)で示される化合物のほかに、1,3,4−トリフェニル−2,3,4,5−テトラヒドロ−1H−1,2,4−トリアゾール−5−イリデン、1,3−ジシクロヘキシルヘキサヒドロピリミジン−2−イリデン、N,N,N’,N’−テトライソプロピルホルムアミジニリデン、1,3,4−トリフェニル−4,5−ジヒドロ−1H−1,2,4−トリアゾール−5−イリデン、及び3−(2,6−ジイソプロピルフェニル)−2,3−ジヒドロチアゾール−2−イリデンなどのヘテロ原子含有カルベン化合物も用い得る。 In addition to the compound represented by the formula (3) or formula (4), 1,3,4-triphenyl-2,3,4,5-tetrahydro-1H-1,2,4-triazole-5 -Iridene, 1,3-dicyclohexylhexahydropyrimidin-2-ylidene, N, N, N ', N'-tetraisopropylformamidinylidene, 1,3,4-triphenyl-4,5-dihydro-1H- Heteroatom-containing carbene compounds such as 1,2,4-triazole-5-ylidene and 3- (2,6-diisopropylphenyl) -2,3-dihydrothiazol-2-ylidene can also be used.
前記式(1)及び(2)において、アニオン(陰イオン)性配位子X1、X2は、中心原子から引き離されたときに負の電荷を持つ配位子である。例えば、弗素原子(F)、塩素原子(Cl)、臭素原子(Br)、及び沃素原子(I)などのハロゲン原子、ジケトネート基、置換シクロペンタジエニル基、アルコキシ基、アリールオキシ基、及びカルボキシル基などを挙げることができる。これらの中でもハロゲン原子が好ましく、塩素原子がより好ましい。 In the formulas (1) and (2), the anionic (anionic) ligands X 1 and X 2 are ligands having a negative charge when separated from the central atom. For example, halogen atoms such as fluorine atom (F), chlorine atom (Cl), bromine atom (Br), and iodine atom (I), diketonate group, substituted cyclopentadienyl group, alkoxy group, aryloxy group, and carboxyl Examples include groups. Among these, a halogen atom is preferable and a chlorine atom is more preferable.
また、中性電子供与性化合物は、中心原子から引き離されたときに中性の電荷を持つ配位子であればいかなるものでもよい。その具体例としては、カルボニル類、アミン類、ピリジン類、エーテル類、ニトリル類、エステル類、ホスフィン類、チオエーテル類、芳香族化合物、オレフィン類、イソシアニド類、及びチオシアネート類などが挙げられる。これらの中でも、ホスフィン類、エーテル類及びピリジン類が好ましく、トリアルキルホスフィンがより好ましい。 The neutral electron-donating compound may be any ligand as long as it has a neutral charge when it is separated from the central atom. Specific examples thereof include carbonyls, amines, pyridines, ethers, nitriles, esters, phosphines, thioethers, aromatic compounds, olefins, isocyanides, and thiocyanates. Among these, phosphines, ethers and pyridines are preferable, and trialkylphosphine is more preferable.
前記式(1)で表されるルテニウムカルベン錯体としては、ベンジリデン(1,3−ジメシチル−4−イミダゾリジン−2−イリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、ベンジリデン(1,3−ジメシチル−4,5−ジブロモ−4−イミダゾリン−2−イリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、(1,3−ジメシチル−4−イミダゾリン−2−イリデン)(3−フェニル−1H−インデン−1−イリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、(1,3−ジメシチルイミダゾリジン−2−イリデン)(3−メチル−2−ブテン−1−イリデン)(トリシクロペンチルホスフィン)ルテニウムジクロリド、ベンジリデン(1,3−ジメシチル−オクタヒドロベンズイミダゾール−2−イリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、ベンジリデン[1,3−ジ(1−フェニルエチル)−4−イミダゾリン−2−イリデン](トリシクロヘキシルホスフィン)ルテニウムジクロリド、ベンジリデン(1,3−ジメシチル−2,3−ジヒドロベンズイミダゾール−2−イリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、ベンジリデン(トリシクロヘキシルホスフィン)(1,3,4−トリフェニル−2,3,4,5−テトラヒドロ−1H−1,2,4−トリアゾール−5−イリデン)ルテニウムジクロリド、(1,3−ジイソプロピルヘキサヒドロピリミジン−2−イリデン)(エトキシメチレン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、ベンジリデン(1,3−ジメシチルイミダゾリジン−2−イリデン)ピリジンルテニウムジクロリド、(1,3−ジメシチルイミダゾリジン−2−イリデン)(2−フェニルエチリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、(1,3−ジメシチル−4−イミダゾリン−2−イリデン)(2−フェニルエチリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、(1,3−ジメシチル−4,5−ジブロモ−4−イミダゾリン−2−イリデン)[(フェニルチオ)メチレン](トリシクロヘキシルホスフィン)ルテニウムジクロリド、及び(1,3−ジメシチル−4,5−ジブロモ−4−イミダゾリン−2−イリデン)(2−ピロリドン−1−イルメチレン)(トリシクロヘキシルホスフィン)ルテニウムジクロリドなどの、ヘテロ原子含有カルベン化合物及び中性の電子供与性化合物が各々1つ結合したルテニウムカルベン錯体; Examples of the ruthenium carbene complex represented by the formula (1) include benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl-4, 5-dibromo-4-imidazoline-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4-imidazoline-2-ylidene) (3-phenyl-1H-indene-1-ylidene) (tri Cyclohexylphosphine) ruthenium dichloride, (1,3-dimesitylimidazolidine-2-ylidene) (3-methyl-2-buten-1-ylidene) (tricyclopentylphosphine) ruthenium dichloride, benzylidene (1,3-dimesityl- Octahydrobenzi Dazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene [1,3-di (1-phenylethyl) -4-imidazoline-2-ylidene] (tricyclohexylphosphine) ruthenium dichloride, benzylidene (1,3- Dimesityl-2,3-dihydrobenzimidazol-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride, benzylidene (tricyclohexylphosphine) (1,3,4-triphenyl-2,3,4,5-tetrahydro-1H- 1,2,4-triazol-5-ylidene) ruthenium dichloride, (1,3-diisopropylhexahydropyrimidin-2-ylidene) (ethoxymethylene) (tricyclohexylphosphine) ruthenium dichloride, benzylid (1,3-Dimesitylimidazolidin-2-ylidene) pyridine ruthenium dichloride, (1,3-Dimesitylimidazolidin-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, 1,3-Dimesityl-4-imidazoline-2-ylidene) (2-phenylethylidene) (tricyclohexylphosphine) ruthenium dichloride, (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) [ (Phenylthio) methylene] (tricyclohexylphosphine) ruthenium dichloride and (1,3-dimesityl-4,5-dibromo-4-imidazoline-2-ylidene) (2-pyrrolidone-1-ylmethylene) (tricyclohexylphosphine) ruthenium Dichloride Which is a ruthenium carbene complex in which a heteroatom-containing carbene compound and a neutral electron-donating compound are each bonded;
ベンジリデンビス(トリシクロヘキシルホスフィン)ルテニウムジクロリドや(3−メチル−2−ブテン−1−イリデン)ビス(トリシクロペンチルホスフィン)ルテニウムジクロリドなどの、2つの中性電子供与性化合物が結合したルテニウムカルベン錯体; A ruthenium carbene complex in which two neutral electron donating compounds such as benzylidenebis (tricyclohexylphosphine) ruthenium dichloride and (3-methyl-2-buten-1-ylidene) bis (tricyclopentylphosphine) ruthenium dichloride are bonded;
ベンジリデンビス(1,3−ジシクロヘキシルイミダゾリジン−2−イリデン)ルテニウムジクロリドやベンジリデンビス(1,3−ジイソプロピル−4−イミダゾリン−2−イリデン)ルテニウムジクロリドなどの、2つのヘテロ原子含有カルベン化合物が結合したルテニウムカルベン錯体;などが挙げられる。 Two heteroatom-containing carbene compounds such as benzylidenebis (1,3-dicyclohexylimidazolidine-2-ylidene) ruthenium dichloride and benzylidenebis (1,3-diisopropyl-4-imidazoline-2-ylidene) ruthenium dichloride bonded together Ruthenium carbene complex; and the like.
前記式(2)で表されるルテニウムカルベン錯体としては、(1,3−ジメシチルイミダゾリジン−2−イリデン)(フェニルビニリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド、(t−ブチルビニリデン)(1,3−ジイソプロピル−4−イミダゾリン−2−イリデン)(トリシクロペンチルホスフィン)ルテニウムジクロリド、及びビス(1,3−ジシクロヘキシル−4−イミダゾリン−2−イリデン)フェニルビニリデンルテニウムジクロリドなどが挙げられる。 Examples of the ruthenium carbene complex represented by the formula (2) include (1,3-dimesitylmimidazolidine-2-ylidene) (phenylvinylidene) (tricyclohexylphosphine) ruthenium dichloride, (t-butylvinylidene) (1 , 3-diisopropyl-4-imidazoline-2-ylidene) (tricyclopentylphosphine) ruthenium dichloride, bis (1,3-dicyclohexyl-4-imidazoline-2-ylidene) phenylvinylidene ruthenium dichloride, and the like.
これらのルテニウムカルベン錯体の中でも、前記式(1)で表され、かつ配位子として前記式(4)で表される化合物を1つ有するものが最も好ましい。 Among these ruthenium carbene complexes, those having one compound represented by the formula (1) and represented by the formula (4) as a ligand are most preferable.
これらのルテニウムカルベン錯体は、Org. Lett., 1999年, 第1巻, 953頁や、Tetrahedron. Lett., 1999年, 第40巻, 2247頁などに記載された方法によって製造することができる。 These ruthenium carbene complexes can be produced by the methods described in Org. Lett., 1999, Vol. 1, page 953, Tetrahedron. Lett., 1999, Vol. 40, page 2247, and the like.
前記メタセシス重合触媒は、それぞれ単独で、あるいは2種以上を組み合わせて用いられる。メタセシス重合触媒の使用量は、モル比(メタセシス重合触媒中の金属原子:シクロオレフィンモノマー)で、通常、1:2,000〜1:2,000,000、好ましくは1:5,000〜1:1,000,000、より好ましくは1:10,000〜1:500,000の範囲である。 The metathesis polymerization catalysts may be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst used is a molar ratio (metal atom in the metathesis polymerization catalyst: cycloolefin monomer) and is usually from 1: 2,000 to 1: 2,000,000, preferably from 1: 5,000 to 1. : 1,000,000, more preferably in the range of 1: 10,000 to 1: 500,000.
メタセシス重合触媒は所望により、少量の不活性溶媒に溶解又は懸濁して使用することができる。かかる溶媒としては、n−ペンタン、n−ヘキサン、n−ヘプタン、流動パラフィン、及びミネラルスピリットなどの鎖状脂肪族炭化水素;シクロペンタン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、トリメチルシクロヘキサン、エチルシクロヘキサン、ジエチルシクロヘキサン、デカヒドロナフタレン、ジシクロヘプタン、トリシクロデカン、ヘキサヒドロインデン、及びシクロオクタンなどの脂環式炭化水素;ベンゼン、トルエン、及びキシレンなどの芳香族炭化水素;インデンやテトラヒドロナフタレンなどの脂環と芳香環とを有する炭化水素;ニトロメタン、ニトロベンゼン、及びアセトニトリルなどの含窒素炭化水素;ジエチルエーテルやテトラヒドロフランなどの含酸素炭化水素;などが挙げられる。これらの中では、鎖状脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、及び脂環と芳香環とを有する炭化水素の使用が好ましい。 If desired, the metathesis polymerization catalyst can be used dissolved or suspended in a small amount of an inert solvent. Such solvents include chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, liquid paraffin, and mineral spirits; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethyl Cycloaliphatic hydrocarbons such as cyclohexane, decahydronaphthalene, dicycloheptane, tricyclodecane, hexahydroindene and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic rings such as indene and tetrahydronaphthalene And hydrocarbons having an aromatic ring; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, and acetonitrile; oxygen-containing hydrocarbons such as diethyl ether and tetrahydrofuran; Among these, it is preferable to use a chain aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, and a hydrocarbon having an alicyclic ring and an aromatic ring.
(架橋剤)
本発明に使用される架橋剤は、本発明の重合性組成物を重合反応に供して得られる重合体(シクロオレフィンポリマー)において架橋反応を誘起する目的で使用される。従って、該重合体は、後架橋可能な熱可塑性樹脂となりうる。ここで「後架橋可能な」とは、該樹脂を加熱することにより架橋反応を進行させて架橋樹脂になし得ることを意味する。前記重合体を基材樹脂とする本発明の架橋性樹脂成形体は、加熱により溶融するが、高粘度であるため、その形状は保持する一方、任意の部材を接触させた場合、その表面では、該部材の形状に対し樹脂が追従性を発揮し、最終的に架橋して硬化する。本発明の架橋性樹脂成形体のかかる特性は、本発明の架橋性樹脂成形体を積層し、加熱して溶融、架橋して得られる積層体において層間密着性及び配線埋め込み性の発現に寄与するものと考えられる。
(Crosslinking agent)
The crosslinking agent used in the present invention is used for the purpose of inducing a crosslinking reaction in a polymer (cycloolefin polymer) obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction. Accordingly, the polymer can be a post-crosslinkable thermoplastic resin. Here, “after-crosslinking is possible” means that the resin can be heated to advance a crosslinking reaction to form a crosslinked resin. Although the crosslinkable resin molded product of the present invention using the polymer as a base resin melts by heating, it retains its shape because of its high viscosity. On the other hand, when an arbitrary member is contacted, The resin exhibits followability to the shape of the member, and finally crosslinks and cures. Such characteristics of the crosslinkable resin molded article of the present invention contribute to the development of interlayer adhesion and wiring embedding in a laminate obtained by laminating, melting, and crosslinking the crosslinkable resin molded article of the present invention. It is considered a thing.
本発明において架橋剤としては、特に限定されないが、通常、ラジカル発生剤が好適に用いられる。ラジカル発生剤としては、例えば、有機過酸化物、ジアゾ化合物、及び非極性ラジカル発生剤などが挙げられ、好ましくは有機過酸化物、及び非極性ラジカル発生剤である。 Although it does not specifically limit as a crosslinking agent in this invention, Usually, a radical generator is used suitably. Examples of the radical generator include organic peroxides, diazo compounds, and nonpolar radical generators, and organic peroxides and nonpolar radical generators are preferable.
有機過酸化物としては、例えば、t−ブチルヒドロペルオキシド、p−メンタンヒドロペルオキシド、及びクメンヒドロペルオキシドなどのヒドロペルオキシド類;ジクミルペルオキシド、t−ブチルクミルペルオキシド、α,α’−ビス(t−ブチルペルオキシ−m−イソプロピル)ベンゼン、ジ−t−ブチルペルオキシド、2,5−ジメチル−2,5−ジ(t−ブチルペルオキシ)−3−ヘキシン、及び2,5−ジメチル−2,5−ジ(t−ブチルペルオキシ)ヘキサンなどのジアルキルペルオキシド類;ジプロピオニルペルオキシドやベンゾイルペルオキシドなどのジアシルペルオキシド類;2,2−ジ(t−ブチルペルオキシ)ブタン、1,1−ジ(t−ヘキシルペルオキシ)シクロヘキサン、1,1−ジ(t−ブチルペルオキシ)−2−メチルシクロヘキサン、及び1,1−ジ(t−ブチルペルオキシ)シクロヘキサンなどのペルオキシケタール類;t−ブチルペルオキシアセテートやt−ブチルペルオキシベンゾエートなどのペルオキシエステル類;t−ブチルペルオキシイソプロピルカルボナートやジ(イソプロピルペルオキシ)ジカルボナートなどのペルオキシカルボナート類;t−ブチルトリメチルシリルペルオキシドなどのアルキルシリルペルオキシド類;3,3,5,7,7−ペンタメチル−1,2,4−トリオキセパン、3,6,9−トリエチル−3,6,9−トリメチル−1,4,7−トリパーオキソナン、及び3,6−ジエチル−3,6−ジメチル−1,2,4,5−テトロキサンなどの環状パーオキサイド類;が挙げられる。中でも、重合反応に対する障害が少ない点で、ジアルキルペルオキシド類、ペルオキシケタール類、及び環状パーオキサイド類が好ましい。 Examples of the organic peroxide include hydroperoxides such as t-butyl hydroperoxide, p-menthane hydroperoxide, and cumene hydroperoxide; dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t -Butylperoxy-m-isopropyl) benzene, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, and 2,5-dimethyl-2,5- Dialkyl peroxides such as di (t-butylperoxy) hexane; diacyl peroxides such as dipropionyl peroxide and benzoyl peroxide; 2,2-di (t-butylperoxy) butane, 1,1-di (t-hexylperoxy) Cyclohexane, 1,1-di (t-butylperoxy)- Peroxyketals such as 2-methylcyclohexane and 1,1-di (t-butylperoxy) cyclohexane; peroxyesters such as t-butylperoxyacetate and t-butylperoxybenzoate; t-butylperoxyisopropylcarbonate and di Peroxycarbonates such as (isopropylperoxy) dicarbonate; alkylsilyl peroxides such as t-butyltrimethylsilyl peroxide; 3,3,5,7,7-pentamethyl-1,2,4-trioxepane, 3,6,9- Cyclic peroxides such as triethyl-3,6,9-trimethyl-1,4,7-triperoxonan and 3,6-diethyl-3,6-dimethyl-1,2,4,5-tetroxane; Is mentioned. Among these, dialkyl peroxides, peroxyketals, and cyclic peroxides are preferable in that there are few obstacles to the polymerization reaction.
ジアゾ化合物としては、例えば、4,4’−ビスアジドベンザル(4−メチル)シクロヘキサノンや2,6−ビス(4’−アジドベンザル)シクロヘキサノンなどが挙げられる。 Examples of the diazo compound include 4,4'-bisazidobenzal (4-methyl) cyclohexanone and 2,6-bis (4'-azidobenzal) cyclohexanone.
非極性ラジカル発生剤としては、2,3−ジメチル−2,3−ジフェニルブタン、3,4−ジメチル−3,4−ジフェニルヘキサン、1,1,2−トリフェニルエタン、及び1,1,1−トリフェニル−2−フェニルエタンなどが挙げられる。 Nonpolar radical generators include 2,3-dimethyl-2,3-diphenylbutane, 3,4-dimethyl-3,4-diphenylhexane, 1,1,2-triphenylethane, and 1,1,1 -Triphenyl-2-phenylethane and the like.
ラジカル発生剤を架橋剤として使用する場合、1分間半減期温度は、硬化(本発明の重合性組成物を重合反応に供して得られる重合体の架橋)の条件により適宜選択されるが、通常、100〜300℃、好ましくは150〜250℃、より好ましくは160〜230℃の範囲である。ここで1分間半減期温度は、ラジカル発生剤の半量が1分間で分解する温度である。ラジカル発生剤の1分間半減期温度は、例えば、各ラジカル発生剤メーカー(例えば、日本油脂株式会社)のカタログやホームページを参照すればよい。 When a radical generator is used as a crosslinking agent, the half-life temperature for 1 minute is appropriately selected depending on the conditions of curing (crosslinking of a polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction). , 100 to 300 ° C, preferably 150 to 250 ° C, more preferably 160 to 230 ° C. Here, the half-life temperature for 1 minute is a temperature at which half of the radical generator decomposes in 1 minute. The 1-minute half-life temperature of the radical generator may be referred to, for example, a catalog or homepage of each radical generator manufacturer (for example, Nippon Oil & Fats Co., Ltd.).
前記ラジカル発生剤は、それぞれ単独で、又は2種以上を組み合わせて用いることができる。本発明の重合性組成物へのラジカル発生剤の配合量としては、シクロオレフィンモノマー100重量部に対して、通常、0.01〜10重量部、好ましくは0.1〜10重量部、より好ましくは0.5〜5重量部の範囲である。 The radical generators can be used alone or in combination of two or more. The amount of radical generator added to the polymerizable composition of the present invention is usually 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 100 parts by weight of cycloolefin monomer. Is in the range of 0.5 to 5 parts by weight.
(架橋助剤)
本発明の重合性組成物には、ビニリデン基を1つ有する一官能化合物(以下、単に一官能化合物という場合がある。)、ビニリデン基を2つ有する二官能化合物(以下、単に二官能化合物という場合がある。)、及びビニリデン基を3つ有する三官能化合物(以下、単に三官能化合物という場合がある。)が用いられるが、これらの化合物は、本発明の重合性組成物を重合反応に供して得られる重合体の架橋を促進する架橋助剤として機能する。これらの化合物はいずれも、開環重合反応には関与しないが、ビニリデン基により、架橋剤で誘起される架橋反応に関与しうる。本発明の重合性組成物において、これらの一官能化合物、二官能化合物、及び三官能化合物は、重量比(一官能化合物:二官能化合物:三官能化合物)で1〜20:0.1〜20:10〜25の含有割合で用いられる。
(Crosslinking aid)
The polymerizable composition of the present invention includes a monofunctional compound having one vinylidene group (hereinafter sometimes simply referred to as a monofunctional compound) and a bifunctional compound having two vinylidene groups (hereinafter simply referred to as a bifunctional compound). And trifunctional compounds having three vinylidene groups (hereinafter sometimes simply referred to as trifunctional compounds) are used, and these compounds are used in the polymerization reaction of the polymerizable composition of the present invention. It functions as a crosslinking aid for accelerating crosslinking of the polymer obtained. None of these compounds participate in the ring-opening polymerization reaction, but can participate in the crosslinking reaction induced by the crosslinking agent by the vinylidene group. In the polymerizable composition of the present invention, these monofunctional compound, bifunctional compound, and trifunctional compound are 1-20: 0.1-20 in weight ratio (monofunctional compound: bifunctional compound: trifunctional compound). : Used in a content ratio of 10 to 25.
前記の通り、本発明の重合性組成物を重合反応に供して得られる重合体は、後架橋可能な熱可塑性樹脂となりうる。本発明の架橋性樹脂成形体は、かかる重合体を基材樹脂とするものである。
本発明に使用する一官能化合物、二官能化合物及び三官能化合物はいずれも、本発明の架橋性樹脂成形体を構成する重合体中、実質的に遊離の状態で存在しており、従って、該重合体に対し可塑効果を発現する。そのため、該成形体を加熱すると重合体が溶融し、適度な流動性を示す。一方、該成形体の加熱を続けると架橋剤により架橋反応が誘起されるが、一官能化合物、二官能化合物及び三官能化合物はいずれも、架橋反応に関与して重合体への結合反応性を示すことから、架橋反応の進行と共に、遊離の状態で存在するものが減少し、架橋反応の終了時点では、重合体に結合するものと推定される。一官能化合物、二官能化合物及び三官能化合物は上記の通りの特性を示すが、重合体への結合反応性は一官能化合物<二官能化合物<三官能化合物の順で高いようであり、従って、可塑効果は、三官能化合物<二官能化合物<一官能化合物の順で長く発現されうる。架橋助剤は、得られる積層体において架橋密度を高め、積層体の耐熱性を向上させる意図で用いられるが、架橋性樹脂成形体の加熱時に、該成形体を構成する重合体で、より早期に架橋構造が形成されると充分な重合体の流動性が得られず、架橋性樹脂成形体表面の、他の部材に対する樹脂の追従性が低下する。その点、一官能化合物、二官能化合物及び三官能化合物を組合わせて用いると、重合体において、三官能化合物による可塑効果の発現が消失した後においても、一官能化合物や二官能化合物による可塑効果の持続的発現が期待でき、得られる積層体では、配線埋め込み性、及び耐熱性が非常にバランス良く向上することになる。
すなわち、本発明においては、得られる積層体において配線埋め込み性の向上に寄与する、硬化時における基材樹脂の適度な流動性の発現と、得られる積層体において耐熱性の向上に寄与する、硬化後の基材樹脂の架橋密度の増加、という相反する物理現象を、所定の一官能化合物、二官能化合物及び三官能化合物を前記範囲の含有割合で組合わせて用いることにより両立させている。
反対に、それらの一官能化合物、二官能化合物及び三官能化合物を前記範囲の含有割合で用いない場合、一官能化合物の割合が過剰であると、得られる積層体に一官能化合物が残存して揮発成分となり、耐熱性及びめっき性が不充分になり、一官能化合物の割合が不足すると、積層体で充分な配線埋め込み性が得られない、また、二官能化合物の割合が過剰であると、得られる積層体において誘電正接が悪化し、二官能化合物の割合が不足すると、積層体で充分な配線埋め込み性が得られない、さらに、三官能化合物の割合が過剰であると、得られる積層体において誘電正接が悪化し、三官能化合物の割合が不足すると、積層体で充分な耐熱性が得られない。
As described above, the polymer obtained by subjecting the polymerizable composition of the present invention to a polymerization reaction can be a post-crosslinkable thermoplastic resin. The crosslinkable resin molded article of the present invention uses such a polymer as a base resin.
All of the monofunctional compound, bifunctional compound and trifunctional compound used in the present invention are present in a substantially free state in the polymer constituting the crosslinkable resin molded article of the present invention. A plasticizing effect is exerted on the polymer. Therefore, when the molded body is heated, the polymer melts and exhibits an appropriate fluidity. On the other hand, when the molded body is continuously heated, a crosslinking reaction is induced by the crosslinking agent. However, the monofunctional compound, the bifunctional compound, and the trifunctional compound are all involved in the crosslinking reaction and have a binding reactivity to the polymer. As shown, as the cross-linking reaction proceeds, the amount existing in a free state decreases, and it is presumed that the polymer is bonded to the polymer at the end of the cross-linking reaction. The monofunctional compound, the bifunctional compound and the trifunctional compound exhibit the characteristics as described above, but the binding reactivity to the polymer seems to be higher in the order of monofunctional compound <bifunctional compound <trifunctional compound. The plastic effect can be expressed for a long time in the order of trifunctional compound <bifunctional compound <monofunctional compound. The crosslinking aid is used for the purpose of increasing the crosslink density in the resulting laminate and improving the heat resistance of the laminate, but is a polymer that constitutes the molded body when the crosslinkable resin molded body is heated. If a cross-linked structure is formed, sufficient polymer fluidity cannot be obtained, and the followability of the resin to other members on the surface of the cross-linkable resin molded product is lowered. In that regard, when a monofunctional compound, a bifunctional compound, and a trifunctional compound are used in combination, the plastic effect of the monofunctional compound or the bifunctional compound is lost even after the plastic effect of the trifunctional compound disappears in the polymer. In the laminated body obtained, the wiring embedding property and the heat resistance are improved in a very balanced manner.
That is, in the present invention, it contributes to improving the wiring embedding property in the obtained laminate, exhibits appropriate fluidity of the base resin during curing, and contributes to improving the heat resistance in the obtained laminate. The contradictory physical phenomenon of increasing the crosslinking density of the base resin later is made compatible by using a predetermined monofunctional compound, bifunctional compound and trifunctional compound in combination in the above-mentioned content ratio.
On the contrary, when these monofunctional compounds, bifunctional compounds and trifunctional compounds are not used in the above-mentioned content ratio, if the proportion of the monofunctional compound is excessive, the monofunctional compound remains in the obtained laminate. If it becomes a volatile component, heat resistance and plating properties become insufficient, and the proportion of monofunctional compounds is insufficient, sufficient wiring embedding cannot be obtained in the laminate, and if the proportion of bifunctional compounds is excessive, If the dielectric loss tangent is deteriorated in the obtained laminate and the ratio of the bifunctional compound is insufficient, sufficient wiring embedding cannot be obtained in the laminate, and further, if the proportion of the trifunctional compound is excessive, the resulting laminate is obtained. If the dielectric loss tangent deteriorates and the ratio of the trifunctional compound is insufficient, sufficient heat resistance cannot be obtained in the laminate.
本発明に使用する一官能化合物、二官能化合物及び三官能化合物において、ビニリデン基は、架橋反応性に優れることから、イソプロペニル基又はメタクリル基として存在するのが好ましく、メタクリル基として存在するのがより好ましい。
ビニリデン基を1つ有する一官能化合物の具体例としては、イソプロペニルベンゼン、2-イソプロペニルトルエン、4-イソプロペニルトルエン、2-イソプロペニルナフタレン、イソプロペニルオキシトリメチルシラン、及び酢酸イソプロペニルなどの、イソプロペニル基を1つ有する一官能化合物;及びベンジルメタクリレート、ヘキシルメタクリレート、フェニルメタクリレート、フェノキシエチルメタクリレートオクテニルメタクリレート、トリルメタクリレート、シクロヘキシルメタクリレート、アダマンチルメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、テトラヒドロフルフリルメタクリレート、メトキシジエチレングリコールメタクリレート、ジシクロペンテニルオキシエチルメタクリレート、及びジシクロペンタニルメタクリレートなどの、メタクリル基を1つ有する一官能化合物;などが挙げられる。ビニリデン基を1つ有する一官能化合物としては、メタクリル基を1つ有する一官能化合物(一官能メタクリレート化合物)が好ましい。
ビニリデン基を2つ有する二官能化合物の具体例としては、p−ジイソプロペニルベンゼン、m−ジイソプロペニルベンゼン、及びo−ジイソプロペニルベンゼンなどの、イソプロペニル基を2つ有する二官能化合物;エチレンジメタクリレート、1,3−ブチレンジメタクリレート、1,4−ブチレンジメタクリレート、1,6−ヘキサンジオールジメタクリレート、ポリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ビスフェノールジメタクリレート、トリシクロデカンジメタノールジメタクリレート、1、3―アダマンチルジメタノールジメタクリレート、1、4−アダマンチルジメタノールジメタクリレート、及び2,2’−ビス(4−メタクリロキシジエトキシフェニル)プロパンなどの、メタクリル基を2つ有する二官能化合物などが挙げられる。ビニリデン基を2つ有する二官能化合物としては、メタクリル基を2つ有する二官能化合物(二官能メタクリレート化合物)が好ましい。
ビニリデン基を3つ有する三官能化合物の具体例としては、トリメチロ−ルプロパントリメタクリレートやペンタエリトリトールトリメタクリレートなどの、メタクリル基を3つ有する三官能化合物などが挙げられる。ビニリデン基を3つ有する三官能化合物としては、メタクリル基を3つ有する三官能化合物(三官能メタクリレート化合物)が好ましい。
In the monofunctional compound, the bifunctional compound and the trifunctional compound used in the present invention, the vinylidene group is preferably present as an isopropenyl group or a methacryl group, and preferably present as a methacryl group, because of excellent crosslinking reactivity. More preferred.
Specific examples of monofunctional compounds having one vinylidene group include isopropenylbenzene, 2-isopropenyltoluene, 4-isopropenyltoluene, 2-isopropenylnaphthalene, isopropenyloxytrimethylsilane, and isopropenyl acetate. Monofunctional compounds having one isopropenyl group; and benzyl methacrylate, hexyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate octenyl methacrylate, tolyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, methoxydiethylene glycol Methacrylate, dicyclopentenyloxyethyl methacrylate, and di Such as black dicyclopentanyl methacrylate, monofunctional compound having one methacryl group; and the like. The monofunctional compound having one vinylidene group is preferably a monofunctional compound having one methacryl group (monofunctional methacrylate compound).
Specific examples of the bifunctional compound having two vinylidene groups include bifunctional compounds having two isopropenyl groups, such as p-diisopropenylbenzene, m-diisopropenylbenzene, and o-diisopropenylbenzene; Ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Diethylene glycol dimethacrylate, bisphenol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,3-adamantyl dimethanol dimethacrylate, 1,4-adapter Inch distearate dimethanol dimethacrylate, and 2,2'-bis (4-methacryloxydiethoxyphenyl Siji ethoxyphenyl) propane, and the like bifunctional compounds having two methacryl groups. As the bifunctional compound having two vinylidene groups, a bifunctional compound having two methacrylic groups (bifunctional methacrylate compound) is preferable.
Specific examples of trifunctional compounds having three vinylidene groups include trifunctional compounds having three methacrylic groups such as trimethylolpropane trimethacrylate and pentaerythritol trimethacrylate. The trifunctional compound having three vinylidene groups is preferably a trifunctional compound having three methacrylic groups (trifunctional methacrylate compound).
本発明においては、一官能メタクリレート化合物、二官能メタクリレート化合物及び三官能メタクリレート化合物を前記所定の含有割合で組合せて用いるのが特に好ましく、当該組合せの具体例としては、ベンジルメタクリレート、ヘキシルメタクリレート、フェニルメタクリレート、フェノキシエチルメタクリレートオクテニルメタクリレート、トリルメタクリレート、シクロヘキシルメタクリレート、アダマンチルメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、テトラヒドロフルフリルメタクリレート、メトキシジエチレングリコールメタクリレート、ジシクロペンテニルオキシエチルメタクリレート、及びジシクロペンタニルメタクリレートからなる群から選ばれる少なくとも1つの化合物(以上、一官能メタクリレート化合物)と、エチレンジメタクリレート、1,3−ブチレンジメタクリレート、1,4−ブチレンジメタクリレート、1,6−ヘキサンジオールジメタクリレート、ポリエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、エチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ビスフェノールジメタクリレート、トリシクロデカンジメタノールジメタクリレート、1、3―アダマンチルジメタノールジメタクリレート、1、4−アダマンチルジメタノールジメタクリレート、及び2,2’−ビス(4−メタクリロキシジエトキシフェニル)プロパンからなる群から選ばれる少なくとも1つの化合物(以上、二官能メタクリレート化合物)と、トリメチロ−ルプロパントリメタクリレート(以上、三官能メタクリレート化合物)とからなる組合せが挙げられる。かかる組合せによれば、架橋性樹脂成形体においては、加熱硬化時の樹脂流動性が向上し、該成形体表面の、他の部材に対する樹脂の追従性が高まり、また、積層体においては、配線埋め込み性、耐熱性、及びめっき性が高度にバランスされ、非常に好適である。 In the present invention, it is particularly preferable to use a monofunctional methacrylate compound, a bifunctional methacrylate compound and a trifunctional methacrylate compound in combination at the predetermined content ratio. Specific examples of the combination include benzyl methacrylate, hexyl methacrylate, and phenyl methacrylate. , Phenoxyethyl methacrylate octenyl methacrylate, tolyl methacrylate, cyclohexyl methacrylate, adamantyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, methoxydiethylene glycol methacrylate, dicyclopentenyloxyethyl methacrylate, and dicyclopentanyl methacrylate At least one compound Acrylate compound), ethylene dimethacrylate, 1,3-butylene dimethacrylate, 1,4-butylene dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, bisphenol dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,3-adamantyl dimethanol dimethacrylate, 1,4-adamantyl dimethanol dimethacrylate, and 2,2′-bis (4 -At least one compound selected from the group consisting of (methacryloxydiethoxyphenyl) propane (above, bifunctional methacrylate) And preparative compounds), trimethylolpropane - Le propane trimethacrylate (or include combinations consisting a trifunctional methacrylate compound). According to such a combination, in the crosslinkable resin molded body, the resin fluidity at the time of heat curing is improved, and the followability of the resin to other members on the surface of the molded body is increased. The embedding property, heat resistance, and plating property are highly balanced and very suitable.
本発明の重合性組成物中、前記の通りの、一官能化合物、二官能化合物、及び三官能化合物の含有割合としては、得られる架橋性樹脂成形体の樹脂流動性を高め、また、得られる積層体において耐熱性を向上させる観点から、重量比(一官能化合物:二官能化合物:三官能化合物)で、好ましくは2〜18:2〜18:12〜23であり、より好ましくは4〜16:4〜16:14〜21である。 In the polymerizable composition of the present invention, as described above, the content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is increased and the resin fluidity of the resulting crosslinkable resin molded article is increased. From the viewpoint of improving heat resistance in the laminate, the weight ratio (monofunctional compound: bifunctional compound: trifunctional compound) is preferably 2-18: 2-18: 12-23, more preferably 4-16. : 4-16: 14-21.
前記一官能化合物、二官能化合物及び三官能化合物は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。本発明の重合性組成物への一官能化合物、二官能化合物及び三官能化合物の合計配合量は、シクロオレフィンモノマー100重量部に対して、通常、0.1〜100重量部、好ましくは0.5〜75重量部、より好ましくは1〜50重量部である。 The monofunctional compound, the bifunctional compound, and the trifunctional compound can be used alone or in combination of two or more. The total compounding amount of the monofunctional compound, bifunctional compound and trifunctional compound in the polymerizable composition of the present invention is usually 0.1 to 100 parts by weight, preferably 0.1 to 100 parts by weight of the cycloolefin monomer. 5 to 75 parts by weight, more preferably 1 to 50 parts by weight.
(重合性組成物)
本発明の重合性組成物には、上記する、シクロオレフィンモノマー、重合触媒、架橋剤、一官能化合物、二官能化合物、及び三官能化合物を必須成分として、所望により、充填剤、重合調整剤、重合反応遅延剤、連鎖移動剤、老化防止剤、及びその他の配合剤を添加することができる。
(Polymerizable composition)
In the polymerizable composition of the present invention, the cycloolefin monomer, the polymerization catalyst, the crosslinking agent, the monofunctional compound, the bifunctional compound, and the trifunctional compound described above as essential components, if necessary, a filler, a polymerization regulator, Polymerization reaction retarders, chain transfer agents, anti-aging agents, and other compounding agents can be added.
本発明においては、積層体を高機能化させる観点から、重合性組成物に充填剤を配合するのが好適である。本発明の重合性組成物は、従来、プリプレグや積層体の製造に用いられている、エポキシ樹脂等を溶媒に溶かしてなる重合体ワニスと比べて低粘度であるため、容易に充填剤を高配合することができる。よって、得られる架橋性樹脂成形体や積層体中には、充填剤が、従来のプリプレグ又は積層体の限界含有量を超えて含まれ得る。 In the present invention, it is preferable to add a filler to the polymerizable composition from the viewpoint of enhancing the functionality of the laminate. The polymerizable composition of the present invention has a low viscosity as compared with a polymer varnish obtained by dissolving an epoxy resin or the like in a solvent, which has been conventionally used in the production of prepregs and laminates. Can be blended. Therefore, in the obtained crosslinkable resin molded body or laminate, the filler may be contained exceeding the limit content of the conventional prepreg or laminate.
充填剤としては、有機充填剤及び無機充填剤のいずれをも用いることができる。所望により適宜選択すればよいが、通常、無機充填剤が好適に用いられる。かかる無機充填剤としては、例えば、高誘電フィラー、低線膨張フィラー、ハロゲン難燃剤、及び非ハロゲン難燃剤が挙げられる。 As the filler, any of organic fillers and inorganic fillers can be used. Although it may be appropriately selected as desired, an inorganic filler is usually preferably used. Examples of such inorganic fillers include high dielectric fillers, low linear expansion fillers, halogen flame retardants, and non-halogen flame retardants.
高誘電フィラーとは誘電性が概して高い無機フィラーである。本発明の重合性組成物に配合することで、得られる積層体において誘電正接は小さく、かつ誘電率を大きくできるため、例えば、かかる積層体によれば、低損失で、デバイス設計の小さな回路基板等が得られ、好適である。
高誘電フィラーとしては、工業的に使用されるものであれば格別な限定なく用いることができるが、特に1GHzにて20℃で測定される比誘電率が、通常、5以上、好ましくは10以上、より好ましくは15以上のものが好適である。かかる高誘電フィラーとしては、例えば、ジルコン酸カルシウム、ジルコン酸ストロンチウム、ジルコン酸鉛、及びジルコニアなどのジルコン酸化物;チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸コバルト、チタン酸亜鉛、及びチタニアなどのチタン酸化物;などを挙げることができる。
High dielectric fillers are inorganic fillers that are generally highly dielectric. By blending with the polymerizable composition of the present invention, the resulting laminate can have a low dielectric loss tangent and a large dielectric constant. For example, according to such a laminate, a circuit board with low loss and small device design can be obtained. Etc. are obtained and suitable.
The high dielectric filler can be used without particular limitation as long as it is industrially used, but the relative dielectric constant measured particularly at 1 GHz at 20 ° C. is usually 5 or more, preferably 10 or more. More preferably, 15 or more are suitable. Such high dielectric fillers include, for example, zircon oxides such as calcium zirconate, strontium zirconate, lead zirconate, and zirconia; barium titanate, strontium titanate, calcium titanate, cobalt titanate, zinc titanate, and And titanium oxides such as titania;
低線膨張フィラーとは線膨張係数が概して低い無機フィラーである。本発明の重合性組成物に配合することで、得られる積層体において機械的強度が向上し、線膨張係数を低減させることができ、好適である。
低線膨張フィラーの線膨張係数としては、通常、15ppm/℃以下である。低線膨張フィラーの線膨張係数は、熱機械分析装置(TMA)により測定することができる。かかる低線膨張フィラーとしては、工業的に用いられるものであれば格別な限定なく用いることができる。例えば、シリカ、シリカバルーン、アルミナ、酸化鉄、酸化亜鉛、酸化マグネシウム、酸化すず、酸化ベリリウム、バリウムフェライト、及びストロンチウムフェライト等の無機酸化物;炭酸カルシウム、炭酸マグネシウム、及び炭酸水素ナトリウム等の無機炭酸塩;硫酸カルシウム等の無機硫酸塩;タルク、クレー、マイカ、カオリン、フライアッシュ、モンモリロナイト、ケイ酸カルシウム、ガラス、及びガラスバルーン等の無機ケイ酸塩;などが挙げられ、好ましくはシリカである。
A low linear expansion filler is an inorganic filler having a generally low linear expansion coefficient. By mix | blending with the polymeric composition of this invention, mechanical strength can improve in the laminated body obtained, a linear expansion coefficient can be reduced, and it is suitable.
The linear expansion coefficient of the low linear expansion filler is usually 15 ppm / ° C. or less. The linear expansion coefficient of the low linear expansion filler can be measured by a thermomechanical analyzer (TMA). As such a low linear expansion filler, any industrially used filler can be used without any particular limitation. For example, inorganic oxides such as silica, silica balloon, alumina, iron oxide, zinc oxide, magnesium oxide, tin oxide, beryllium oxide, barium ferrite, and strontium ferrite; inorganic carbonates such as calcium carbonate, magnesium carbonate, and sodium bicarbonate Salt; inorganic sulfates such as calcium sulfate; inorganic silicates such as talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate, glass, and glass balloon; and the like, preferably silica.
ハロゲン難燃剤は、ハロゲン原子を含む難燃性化合物からなる。ハロゲン難燃剤としては、例えば、トリス(2−クロロエチル)ホスフェート、トリス(クロロプロピル)ホスフェート、トリス(ジクロロプロピル)ホスフェート、塩素化ポリスチレン、塩素化ポリエチレン、高塩素化ポリプロピレン、クロロスルホン化ポリエチレン、ヘキサブロモベンゼン、デカブロモジフェニルオキシド、ビス(トリブロモフェノキシ)エタン、1,2−ビス(ペンタブロモフェニル)エタン、テトラブロモビスフェノールS、テトラデカブロモジフェノキシベンゼン、2,2−ビス(4−ヒドロキシ−3,5−ジブロモフェニルプロパン)、ペンタブロモトルエンなどが挙げられる。 The halogen flame retardant is composed of a flame retardant compound containing a halogen atom. Examples of the halogen flame retardant include tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, chlorinated polystyrene, chlorinated polyethylene, highly chlorinated polypropylene, chlorosulfonated polyethylene, and hexabromo. Benzene, decabromodiphenyl oxide, bis (tribromophenoxy) ethane, 1,2-bis (pentabromophenyl) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-hydroxy-3) , 5-dibromophenylpropane), pentabromotoluene and the like.
非ハロゲン難燃剤は、ハロゲン原子を含まない難燃性化合物からなる。本発明の重合性組成物に配合すれば、得られる積層体の難燃性を向上でき、しかも積層体の燃焼時にダイオキシン発生の心配がなく、好適である。非ハロゲン難燃剤としては、工業的に用いられるものであれば格別な限定なく用いることができる。例えば、水酸化アルミニウムや水酸化マグネシウム等の金属水酸化物難燃剤;ジメチルホスフィン酸アルミニウムやジエチルホスフィン酸アルミニウムなどのホスフィン酸塩難燃剤;酸化マグネシウムや酸化アルミニウム等の金属酸化物難燃剤;トリフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、クレジルジフェニルホスフェート、レゾルシノールビス(ジフェニル)ホスフェート、ビスフェノールAビス(ジフェニル)ホスフェート、及びビスフェノールAビス(ジクレジル)ホスフェートなどの、ホスフィン酸塩以外の含燐難燃剤;メラミン誘導体類、グアニジン類、及びイソシアヌル類等の含窒素難燃剤;ポリ燐酸アンモニウム、燐酸メラミン、ポリ燐酸メラミン、ポリ燐酸メラム、燐酸グアニジン、及びフォスファゼン類等の燐及び窒素の双方を含有する難燃剤;三酸化アンチモンなどのアンチモン化合物難燃剤;などが挙げられる。非ハロゲン難燃剤としては、金属水酸化物難燃剤、ホスフィン酸塩難燃剤、及びホスフィン酸塩以外の含燐難燃剤が好ましい。含燐難燃剤としては、トリクレジルホスフェート、レゾルシノールビス(ジフェニル)ホスフェート、ビスフェノールAビス(ジフェニル)ホスフェート、及びビスフェノールAビス(ジクレジル)ホスフェートが特に好ましい。 Non-halogen flame retardants consist of flame retardant compounds that do not contain halogen atoms. When blended with the polymerizable composition of the present invention, the flame retardancy of the resulting laminate can be improved, and there is no concern of dioxin generation when the laminate is burned, which is preferable. Any non-halogen flame retardant can be used without particular limitation as long as it is industrially used. For example, metal hydroxide flame retardants such as aluminum hydroxide and magnesium hydroxide; phosphinate flame retardants such as aluminum dimethylphosphinate and aluminum diethylphosphinate; metal oxide flame retardants such as magnesium oxide and aluminum oxide; triphenyl Phosphorus containing other than phosphinates such as phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, and bisphenol A bis (dicresyl) phosphate Flame retardants; Nitrogen-containing flame retardants such as melamine derivatives, guanidines and isocyanurs; ammonium polyphosphate, melamine phosphate, melamine polyphosphate, melam polyphosphate, guanidinium phosphate , And flame retardants containing both phosphorus and nitrogen phosphazene, and the like; antimony compound flame retardants such as antimony oxide; and the like. As the non-halogen flame retardant, metal hydroxide flame retardant, phosphinate flame retardant, and phosphorus-containing flame retardant other than phosphinate are preferable. As the phosphorus-containing flame retardant, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, and bisphenol A bis (dicresyl) phosphate are particularly preferable.
本発明に使用される充填剤の粒子径(平均粒子径)は、所望により適宜選択すればよいが、粒子を三次元的にみたときの長手方向と短手方向の長さの平均値として、通常、0.001〜50μm、好ましくは0.01〜10μm、より好ましくは0.1〜5μmの範囲である。 The particle size (average particle size) of the filler used in the present invention may be appropriately selected as desired, but as an average value of the length in the longitudinal direction and the short direction when the particles are viewed three-dimensionally, Usually, it is 0.001-50 micrometers, Preferably it is 0.01-10 micrometers, More preferably, it is the range of 0.1-5 micrometers.
以上の充填剤は、それぞれ単独で、又は2種以上を組み合わせて用いることができる。本発明の重合性組成物への配合量は、シクロオレフィンモノマー100重量部に対して、通常、50重量部以上、好ましくは50〜1,000重量部、より好ましくは50〜750重量部、さらに好ましくは100〜500重量部の範囲である。 The above fillers can be used alone or in combination of two or more. The compounding amount in the polymerizable composition of the present invention is usually 50 parts by weight or more, preferably 50 to 1,000 parts by weight, more preferably 50 to 750 parts by weight, based on 100 parts by weight of the cycloolefin monomer. Preferably it is the range of 100-500 weight part.
重合調整剤は、重合活性を制御したり、重合反応率を向上させたりする目的で配合されるものであり、例えば、トリアルコキシアルミニウム、トリフェノキシアルミニウム、ジアルコキシアルキルアルミニウム、アルコキシジアルキルアルミニウム、トリアルキルアルミニウム、ジアルコキシアルミニウムクロリド、アルコキシアルキルアルミニウムクロリド、ジアルキルアルミニウムクロリド、トリアルコキシスカンジウム、テトラアルコキシチタン、テトラアルコキシスズ、及びテトラアルコキシジルコニウムなどが挙げられる。これらの重合調整剤は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。重合調整剤の配合量は、例えば、モル比(メタセシス重合触媒中の金属原子:重合調整剤)で、通常、1:0.05〜1:100、好ましくは1:0.2〜1:20、より好ましくは1:0.5〜1:10の範囲である。 The polymerization regulator is blended for the purpose of controlling the polymerization activity or improving the polymerization reaction rate. For example, trialkoxyaluminum, triphenoxyaluminum, dialkoxyalkylaluminum, alkoxydialkylaluminum, trialkyl Examples include aluminum, dialkoxyaluminum chloride, alkoxyalkylaluminum chloride, dialkylaluminum chloride, trialkoxyscandium, tetraalkoxytitanium, tetraalkoxytin, and tetraalkoxyzirconium. These polymerization regulators can be used alone or in combination of two or more. The blending amount of the polymerization regulator is, for example, in a molar ratio (metal atom in the metathesis polymerization catalyst: polymerization regulator), usually 1: 0.05 to 1: 100, preferably 1: 0.2 to 1:20. More preferably, it is in the range of 1: 0.5 to 1:10.
重合反応遅延剤は、本発明の重合性組成物の粘度増加を抑制し得るものである。従って、重合反応遅延剤を配合してなる重合性組成物は、架橋性樹脂成形体として、例えば、プリプレグを作製する際、容易に繊維状強化材に均一に含浸させることができ、好ましい。重合反応遅延剤としては、トリフェニルホスフィン、トリブチルホスフィン、トリメチルホスフィン、トリエチルホスフィン、ジシクロヘキシルホスフィン、ビニルジフェニルホスフィン、アリルジフェニルホスフィン、トリアリルホスフィン、及びスチリルジフェニルホスフィンなどのホスフィン化合物;アニリンやピリジンなどのルイス塩基;等を用いることができる。その配合量は、所望により適宜調整すればよい。 A polymerization reaction retarder can suppress an increase in viscosity of the polymerizable composition of the present invention. Therefore, a polymerizable composition obtained by blending a polymerization reaction retarder is preferable because, for example, when a prepreg is produced as a crosslinkable resin molded article, the fibrous reinforcing material can be easily impregnated uniformly. Polymerization retarders include phosphine compounds such as triphenylphosphine, tributylphosphine, trimethylphosphine, triethylphosphine, dicyclohexylphosphine, vinyldiphenylphosphine, allyldiphenylphosphine, triallylphosphine, and styryldiphenylphosphine; Lewis such as aniline and pyridine Base; etc. can be used. What is necessary is just to adjust the compounding quantity suitably as needed.
本発明の重合性組成物には、所望により連鎖移動剤を配合することもできる。得られる架橋性樹脂成形体では、その加熱硬化時に表面樹脂の追従性が向上しうるため、かかる成形体を積層し、加熱して溶融、架橋して得られる積層体では、層間密着性及び配線埋め込み性が高まり、好ましい。 A chain transfer agent can be blended with the polymerizable composition of the present invention as desired. In the resulting crosslinkable resin molded article, the followability of the surface resin can be improved during the heat curing, so in the laminate obtained by laminating, melting and crosslinking such a molded article, interlayer adhesion and wiring The embedding property is increased, which is preferable.
連鎖移動剤は、架橋性の炭素−炭素不飽和結合を1以上有していてもよい。連鎖移動剤の具体例としては、1−ヘキセン、2−ヘキセン、スチレン、ビニルシクロヘキサン、アリルアミン、アクリル酸グリシジル、アリルグリシジルエーテル、エチルビニルエーテル、メチルビニルケトン、2−(ジエチルアミノ)エチルアクリレート、及び4−ビニルアニリンなどの、架橋性の炭素−炭素不飽和結合を持たない連鎖移動剤;ジビニルベンゼン、メタクリル酸ビニル、メタクリル酸アリル、メタクリル酸スチリル、アクリル酸アリル、メタクリル酸ウンデセニル、アクリル酸スチリル、及びエチレングリコールジアクリレートなどの、架橋性の炭素−炭素不飽和結合を1つ有する連鎖移動剤;アリルトリビニルシランやアリルメチルジビニルシランなどの、架橋性の炭素−炭素不飽和結合を2以上有する連鎖移動剤などが挙げられる。これらの中でも、得られる積層体において、配線埋め込み性と耐熱性とを高度にバランスさせる観点から、架橋性の炭素−炭素不飽和結合を1以上有するものが好ましく、架橋性の炭素−炭素不飽和結合を1つ有するものがより好ましい。かかる連鎖移動剤の中でも、ビニル基とメタクリル基とを1つずつ有する連鎖移動剤が好ましく、メタクリル酸ビニル、メタクリル酸アリル、メタクリル酸スチリル、及びメタクリル酸ウンデセニルなどが特に好ましい。
これらの連鎖移動剤は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。本発明の重合性組成物への連鎖移動剤の配合量としては、得られる積層体の配線埋め込み性と耐熱性とのバランスを考慮し、シクロオレフィンモノマー100重量部に対して、通常、0.01〜10重量部、好ましくは0.1〜5重量部である。
The chain transfer agent may have one or more crosslinkable carbon-carbon unsaturated bonds. Specific examples of the chain transfer agent include 1-hexene, 2-hexene, styrene, vinylcyclohexane, allylamine, glycidyl acrylate, allyl glycidyl ether, ethyl vinyl ether, methyl vinyl ketone, 2- (diethylamino) ethyl acrylate, and 4- Chain transfer agents having no crosslinkable carbon-carbon unsaturated bonds, such as vinylaniline; divinylbenzene, vinyl methacrylate, allyl methacrylate, styryl methacrylate, allyl acrylate, undecenyl methacrylate, styryl acrylate, and ethylene Chain transfer agent having one crosslinkable carbon-carbon unsaturated bond, such as glycol diacrylate; Chain transfer agent having two or more crosslinkable carbon-carbon unsaturated bonds, such as allyltrivinylsilane and allylmethyldivinylsilane Na And the like. Among these, in the obtained laminate, from the viewpoint of highly balancing wiring embedding property and heat resistance, those having one or more crosslinkable carbon-carbon unsaturated bonds are preferable. Those having one bond are more preferred. Among such chain transfer agents, chain transfer agents having one vinyl group and one methacryl group are preferable, and vinyl methacrylate, allyl methacrylate, styryl methacrylate, and undecenyl methacrylate are particularly preferable.
These chain transfer agents can be used alone or in combination of two or more. As the blending amount of the chain transfer agent to the polymerizable composition of the present invention, the balance between the wiring embedding property and the heat resistance of the obtained laminate is taken into consideration, and is usually 0. 01 to 10 parts by weight, preferably 0.1 to 5 parts by weight.
また、老化防止剤として、フェノール系老化防止剤、アミン系老化防止剤、リン系老化防止剤及びイオウ系老化防止剤からなる群から選ばれる少なくとも1種の老化防止剤を配合することは、架橋反応を阻害しないで、得られる積層体の耐熱性を高度に向上させることができ、好適である。これらの中でも、フェノール系老化防止剤とアミン系老化防止剤が好ましく、フェノール系老化防止剤がより好ましい。これらの老化防止剤は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができる。老化防止剤の使用量は、所望により適宜選択されるが、シクロオレフィンモノマー100重量部に対して、通常、0.0001〜10重量部、好ましくは0.001〜5重量部、より好ましくは0.01〜2重量部の範囲である。 Moreover, as an anti-aging agent, blending at least one anti-aging agent selected from the group consisting of a phenol-based anti-aging agent, an amine-based anti-aging agent, a phosphorus-based anti-aging agent and a sulfur-based anti-aging agent is a cross-linking. It is preferable because the heat resistance of the obtained laminate can be improved to a high degree without inhibiting the reaction. Among these, a phenolic antiaging agent and an amine antiaging agent are preferable, and a phenolic antiaging agent is more preferable. These anti-aging agents can be used alone or in combination of two or more. The amount of the anti-aging agent is appropriately selected as desired, but is usually 0.0001 to 10 parts by weight, preferably 0.001 to 5 parts by weight, and more preferably 0 to 100 parts by weight of the cycloolefin monomer. .01 to 2 parts by weight.
本発明の重合性組成物には、その他の配合剤を配合することができる。その他の配合剤としては、着色剤、光安定剤、及び発泡剤などを用いることができる。着色剤としては、染料や顔料などが用いられる。染料の種類は多様であり、公知のものを適宜選択して使用すればよい。これらのその他の配合剤は、それぞれ単独で、あるいは2種以上を組み合わせて用いることができ、その使用量は、本発明の効果を損ねない範囲で適宜選択される。 Other compounding agents can be blended in the polymerizable composition of the present invention. As other compounding agents, colorants, light stabilizers, foaming agents and the like can be used. As the colorant, a dye or a pigment is used. There are various kinds of dyes, and known ones may be appropriately selected and used. These other compounding agents can be used alone or in combination of two or more, and the amount used is appropriately selected within a range not impairing the effects of the present invention.
本発明の重合性組成物は、上記成分を混合して得ることができる。混合方法としては、常法に従えばよく、例えば、重合触媒を適当な溶媒に溶解若しくは分散させた液(触媒液)を調製し、別にシクロオレフィンモノマーや架橋剤などの必須成分、及び所望によりその他の配合剤等を配合した液(モノマー液)を調製し、該モノマー液に該触媒液を添加し、攪拌することによって調製することができる。 The polymerizable composition of the present invention can be obtained by mixing the above components. As a mixing method, a conventional method may be followed. For example, a liquid (catalyst liquid) in which a polymerization catalyst is dissolved or dispersed in an appropriate solvent is prepared, and other essential components such as a cycloolefin monomer and a crosslinking agent are optionally added. It can be prepared by preparing a liquid (monomer liquid) containing other compounding agents, adding the catalyst liquid to the monomer liquid, and stirring.
(架橋性樹脂成形体)
本発明の架橋性樹脂成形体は、前記重合性組成物を塊状重合することにより得られる。重合性組成物を塊状重合して架橋性樹脂成形体を得る方法としては、例えば、(a)重合性組成物を支持体上に塗布し、次いで塊状重合する方法、(b)重合性組成物を成形型内に注入し、次いで塊状重合する方法、(c)重合性組成物を繊維状強化材に含浸させ、次いで塊状重合する方法などが挙げられる。
(Crosslinkable resin molding)
The crosslinkable resin molded article of the present invention can be obtained by bulk polymerization of the polymerizable composition. Examples of a method for obtaining a crosslinkable resin molded body by bulk polymerization of the polymerizable composition include, for example, (a) a method in which a polymerizable composition is applied on a support and then bulk polymerization, and (b) a polymerizable composition. Are injected into a mold, and then bulk polymerization is performed, and (c) a fibrous reinforcing material is impregnated with a polymerizable composition and then bulk polymerization is performed.
本発明の重合性組成物は低粘度であるため、(a)の方法における塗布は円滑に実施でき、(b)の方法における注入では、複雑形状の空間部であっても迅速に泡かみを起こさずに重合性組成物を行き渡らせることができ、(c)の方法においては、繊維状強化材に対して速やかに満遍なく重合性組成物を含浸させることができる。 Since the polymerizable composition of the present invention has a low viscosity, the application in the method (a) can be carried out smoothly, and in the injection in the method (b), even if it is a space portion having a complicated shape, the foam bite is rapidly formed. The polymerizable composition can be spread without causing it. In the method (c), the fibrous reinforcing material can be impregnated with the polymerizable composition quickly and uniformly.
(a)の方法によれば、フィルム状や板状等の架橋性樹脂成形体が得られる。該成形体の厚さは、通常、15mm以下、好ましくは5mm以下、より好ましくは0.5mm以下、最も好ましくは0.1mm以下である。支持体としては、例えば、ポリテトラフルオロエチレン、ポリエチレンテレフタレート、ポリプロピレン、ポリエチレン、ポリカーボネート、ポリエチレンナフタレート、ポリアリレート、及びナイロンなどの樹脂からなるフィルムや板;鉄、ステンレス、銅、アルミニウム、ニッケル、クロム、金、及び銀などの金属材料からなるフィルムや板;などが挙げられる。中でも、金属箔又は樹脂フィルムの使用が好ましい。金属箔又は樹脂フィルムの厚さは、作業性などの観点から、通常、1〜150μm、好ましくは2〜100μm、より好ましくは3〜75μmである。金属箔としては、その表面が平滑であるものが好ましく、その表面粗度(Rz)としては、AFM(原子間力顕微鏡)により測定される値で、通常、10μm以下、好ましくは5μm以下、より好ましくは3μm以下、さらに好ましくは2μm以下である。金属箔の表面粗度が上記範囲にあれば、例えば、得られる高周波回路基板において、高周波伝送におけるノイズ、遅延、及び伝送ロス等の発生が抑えられ、好ましい。また、金属箔の表面は、シランカップリング剤、チオールカップリング剤、及びチタネートカップリング剤などの公知のカップリング剤や接着剤などで処理されているのが好ましい。(a)の方法によれば、例えば、支持体として銅箔を用いた場合、樹脂付き銅箔〔Resin Coated Copper (RCC)〕を得ることができる。 According to the method (a), a crosslinkable resin molded product such as a film or plate can be obtained. The thickness of the molded body is usually 15 mm or less, preferably 5 mm or less, more preferably 0.5 mm or less, and most preferably 0.1 mm or less. Examples of the support include films and plates made of resins such as polytetrafluoroethylene, polyethylene terephthalate, polypropylene, polyethylene, polycarbonate, polyethylene naphthalate, polyarylate, and nylon; iron, stainless steel, copper, aluminum, nickel, chromium And films and plates made of metal materials such as gold, silver, and the like. Among these, use of a metal foil or a resin film is preferable. The thickness of the metal foil or resin film is usually 1 to 150 μm, preferably 2 to 100 μm, more preferably 3 to 75 μm, from the viewpoint of workability and the like. The metal foil preferably has a smooth surface, and the surface roughness (Rz) is a value measured by an AFM (atomic force microscope) and is usually 10 μm or less, preferably 5 μm or less. Preferably it is 3 micrometers or less, More preferably, it is 2 micrometers or less. If the surface roughness of the metal foil is in the above range, for example, in the obtained high-frequency circuit board, generation of noise, delay, transmission loss and the like in high-frequency transmission is suppressed, which is preferable. The surface of the metal foil is preferably treated with a known coupling agent or adhesive such as a silane coupling agent, a thiol coupling agent, and a titanate coupling agent. According to the method (a), for example, when a copper foil is used as the support, a resin-coated copper foil (Resin Coated Copper (RCC)) can be obtained.
支持体上に本発明の重合性組成物を塗布する方法としては、スプレーコート法、ディップコート法、ロールコート法、カーテンコート法、ダイコート法、及びスリットコート法などの公知の塗布方法が挙げられる。 Examples of the method for applying the polymerizable composition of the present invention on the support include known coating methods such as spray coating, dip coating, roll coating, curtain coating, die coating, and slit coating. .
支持体上に塗布された重合性組成物を所望により乾燥させ、次いで塊状重合する。塊状重合は重合性組成物を所定の温度で加熱して行われる。重合性組成物の加熱方法としては特に制約されず、支持体に塗布された重合性組成物を、加熱プレート上に載せて加熱する方法、プレス機を用いて加圧しながら加熱(熱プレス)する方法、加熱したローラーで押圧する方法、加熱炉内で加熱する方法などが挙げられる。 The polymerizable composition coated on the support is optionally dried and then bulk polymerized. Bulk polymerization is performed by heating the polymerizable composition at a predetermined temperature. The method for heating the polymerizable composition is not particularly limited, and the polymerizable composition applied to the support is heated on a heating plate, and heated (hot press) while being pressed using a press. Examples thereof include a method, a method of pressing with a heated roller, and a method of heating in a heating furnace.
(b)の方法によれば、任意の形状の架橋性樹脂成形体を得ることができる。その形状としては、シート状、フィルム状、柱状、円柱状、及び多角柱状等が挙げられる。 According to the method (b), a crosslinkable resin molded body having an arbitrary shape can be obtained. Examples of the shape include a sheet shape, a film shape, a column shape, a columnar shape, and a polygonal column shape.
ここで用いる型としては、従来公知の成形型、例えば、割型構造、すなわち、コア型とキャビティー型を有する成形型を用いることができ、それらの空隙部(キャビティー)に重合性組成物を注入して塊状重合させる。コア型とキャビティー型は、目的とする成形品の形状にあった空隙部を形成するように作製される。成形型の形状、材質、大きさなどは特に制限されない。さらに、ガラス板や金属板などの板状成形型と所定の厚さのスペーサーとを用意し、スペーサーを2枚の板状成形型で挟んで形成される空間内に重合性組成物を注入し塊状重合することにより、シート状又はフィルム状の架橋性樹脂成形体を得ることもできる。 As the mold used here, a conventionally known mold, for example, a split mold structure, that is, a mold having a core mold and a cavity mold, can be used, and a polymerizable composition is formed in these voids (cavities). Is injected to cause bulk polymerization. The core mold and the cavity mold are produced so as to form a gap that matches the shape of the target molded product. The shape, material, size, etc. of the mold are not particularly limited. Furthermore, a plate-shaped mold such as a glass plate or a metal plate and a spacer having a predetermined thickness are prepared, and the polymerizable composition is injected into a space formed by sandwiching the spacer between two plate-shaped molds. By carrying out bulk polymerization, a sheet-like or film-like crosslinkable resin molded article can also be obtained.
重合性組成物を成形型のキャビティー内に充填する際の充填圧力(注入圧)は、通常、0.01〜10MPa、好ましくは0.02〜5MPaである。充填圧力が低すぎると、キャビティー内周面に形成された転写面の転写が良好に行われない傾向にあり、充填圧が高すぎると、成形型の剛性を高くしなければならず経済的ではない。型締圧力は、通常、0.01〜10MPaの範囲内である。重合性組成物の加熱方法としては、成形型に配設された電熱器やスチームなどの加熱手段を利用する方法や、成形型を電気炉内で加熱する方法などが挙げられる。 The filling pressure (injection pressure) when filling the polymerizable composition into the cavity of the mold is usually 0.01 to 10 MPa, preferably 0.02 to 5 MPa. If the filling pressure is too low, the transfer surface formed on the inner peripheral surface of the cavity tends not to be transferred well. If the filling pressure is too high, the mold must be rigid and economical. is not. The mold clamping pressure is usually in the range of 0.01 to 10 MPa. Examples of the method for heating the polymerizable composition include a method using a heating means such as an electric heater and steam disposed in the mold, and a method for heating the mold in an electric furnace.
(c)の方法は、シート状又はフィルム状の架橋性樹脂成形体を得るのに好適に使用される。得られる成形体の厚さは、通常、0.001〜10mm、好ましくは0.005〜1mm、より好ましくは0.01〜0.5mmの範囲である。この範囲にあれば、積層時の賦形性、及び積層体の機械的強度や靭性などが向上し、好適である。例えば、重合性組成物の繊維状強化材への含浸は、重合性組成物の所定量を、スプレーコート法、ディップコート法、ロールコート法、カーテンコート法、ダイコート法、及びスリットコート法等の公知の方法により繊維状強化材に塗布し、所望によりその上に保護フィルムを重ね、上側からローラーなどで押圧することにより行うことができる。重合性組成物を繊維状強化材に含浸させた後、含浸物を所定温度に加熱することで重合性組成物を塊状重合させ、所望の架橋性樹脂成形体を得る。架橋性樹脂成形体中、繊維状強化材の含有量としては、通常、10〜90重量%、好ましくは20〜80重量%、より好ましくは30〜70重量%の範囲である。この範囲にあれば、得られる積層体の誘電特性と機械的強度がバランスされ、好適である。 The method (c) is suitably used for obtaining a sheet-like or film-like crosslinkable resin molded article. The thickness of the obtained molded body is usually in the range of 0.001 to 10 mm, preferably 0.005 to 1 mm, more preferably 0.01 to 0.5 mm. If it exists in this range, the shaping property at the time of lamination | stacking and the mechanical strength, toughness, etc. of a laminated body will improve, and it is suitable. For example, the impregnation of the polymerizable composition into the fibrous reinforcing material is performed by using a predetermined amount of the polymerizable composition such as a spray coating method, a dip coating method, a roll coating method, a curtain coating method, a die coating method, and a slit coating method. It can apply by apply | coating to a fibrous reinforcement by a well-known method, stacking a protective film on it as needed, and pressing with a roller etc. from an upper side. After impregnating the polymerizable composition with the fibrous reinforcing material, the impregnated material is heated to a predetermined temperature to cause the polymerizable composition to undergo bulk polymerization to obtain a desired crosslinkable resin molded article. The content of the fibrous reinforcing material in the crosslinkable resin molded body is usually in the range of 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. Within this range, the dielectric properties and mechanical strength of the resulting laminate are balanced, which is preferable.
繊維状強化材としては、無機系及び/又は有機系の繊維が使用できる。例えば、PET(ポリエチレンテレフタレート)繊維、アラミド繊維、超高分子ポリエチレン繊維、ポリアミド(ナイロン)繊維、及び液晶ポリエステル繊維などの有機繊維;ガラス繊維、炭素繊維、アルミナ繊維、タングステン繊維、モリブデン繊維、ブデン繊維、チタン繊維、スチール繊維、ボロン繊維、シリコンカーバイド繊維、及びシリカ繊維などの無機繊維;などが挙げられる。これらの中でも、有機繊維やガラス繊維が好ましく、特にアラミド繊維、液晶ポリエステル繊維、及びガラス繊維が好ましい。ガラス繊維としては、Eガラス、NEガラス、Sガラス、Dガラス、及びHガラス等の繊維を好適に用いることができる。これらは1種単独で、又は2種以上を組合せて用いることができる。繊維状強化材の形態としては、特に限定されず、例えば、マット、クロス、及び不織布などが挙げられる。 As the fibrous reinforcing material, inorganic and / or organic fibers can be used. For example, organic fibers such as PET (polyethylene terephthalate) fiber, aramid fiber, ultra-high molecular polyethylene fiber, polyamide (nylon) fiber, and liquid crystal polyester fiber; glass fiber, carbon fiber, alumina fiber, tungsten fiber, molybdenum fiber, and budene fiber , Inorganic fibers such as titanium fiber, steel fiber, boron fiber, silicon carbide fiber, and silica fiber. Among these, organic fibers and glass fibers are preferable, and aramid fibers, liquid crystal polyester fibers, and glass fibers are particularly preferable. As the glass fiber, fibers such as E glass, NE glass, S glass, D glass, and H glass can be suitably used. These can be used individually by 1 type or in combination of 2 or more types. The form of the fibrous reinforcing material is not particularly limited, and examples thereof include mats, cloths, and nonwoven fabrics.
繊維状強化材に重合性組成物を含浸させてなる含浸物の加熱方法としては、例えば、含浸物を支持体上に設置して前記(a)の方法のようにして加熱する方法、予め型内に繊維状強化材を設置しておき、該型内で重合性組成物を含浸させて含浸物を得、前記(b)の方法のようにして加熱する方法などが挙げられる。 Examples of the heating method of the impregnated product obtained by impregnating the fibrous reinforcing material with the polymerizable composition include, for example, a method in which the impregnated product is placed on a support and heated as in the method (a) above, Examples thereof include a method in which a fibrous reinforcing material is placed in the mold, an impregnated product is obtained by impregnating the polymerizable composition in the mold, and heating is performed as in the method (b).
前記(a)、(b)及び(c)のいずれの方法においても、重合性組成物を重合させるための加熱温度は、通常、30〜250℃、好ましくは50〜200℃、より好ましくは90〜150℃の範囲であって、かつ架橋剤、通常、ラジカル発生剤の1分間半減期温度以下、好ましくは1分間半減期温度の10℃以下、より好ましくは1分間半減期温度の20℃以下である。また、重合時間は適宜選択すればよいが、通常、1秒間〜20分間、好ましくは10秒間〜5分間である。重合性組成物をかかる条件で加熱することにより未反応モノマーの少ない架橋性樹脂成形体が得られるので好適である。 In any of the methods (a), (b) and (c), the heating temperature for polymerizing the polymerizable composition is usually 30 to 250 ° C, preferably 50 to 200 ° C, more preferably 90. In the range of ˜150 ° C. and not more than 1 minute half-life temperature of the crosslinking agent, usually radical generator, preferably not more than 10 ° C. of 1 minute half-life temperature, more preferably not more than 20 ° C. of 1 minute half-life temperature It is. The polymerization time may be appropriately selected, but is usually 1 second to 20 minutes, preferably 10 seconds to 5 minutes. Heating the polymerizable composition under such conditions is preferable because a crosslinkable resin molded article with less unreacted monomer can be obtained.
以上のようにして得られる架橋性樹脂成形体を構成する重合体は、実質的に架橋構造を有さず、例えば、トルエンに可溶である。当該重合体の分子量は、ゲル・パーミエーション・クロマトグラフィー(溶離液:テトラヒドロフラン)で測定されるポリスチレン換算の重量平均分子量で、通常、1,000〜1,000,000、好ましくは5,000〜500,000、より好ましくは10,000〜100,000の範囲である。 The polymer constituting the crosslinkable resin molded article obtained as described above has substantially no crosslink structure and is soluble in, for example, toluene. The molecular weight of the polymer is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (eluent: tetrahydrofuran), and is usually 1,000 to 1,000,000, preferably 5,000 to It is in the range of 500,000, more preferably 10,000 to 100,000.
本発明の架橋性樹脂成形体は、後架橋可能な樹脂成形体であるが、その構成樹脂の一部分が架橋されたものであってもよい。例えば、型内で重合性組成物を塊状重合したときには、型の中心部分は重合反応熱が発散しにくいので、型内の一部の温度が高くなりすぎる場合がある。高温部では架橋反応が起き、架橋が生ずることがある。しかし、熱を発散しやすい表面部が後架橋可能な架橋性の樹脂で形成されていれば、本発明の架橋性樹脂成形体は所望の効果を充分に発揮し得る。 The crosslinkable resin molded article of the present invention is a post-crosslinkable resin molded article, but a part of the constituent resin may be crosslinked. For example, when the polymerizable composition is bulk-polymerized in the mold, the temperature of a part of the mold may become too high because the polymerization reaction heat hardly diffuses in the central part of the mold. In the high temperature part, a cross-linking reaction occurs, and cross-linking may occur. However, if the surface part that easily dissipates heat is formed of a crosslinkable resin that can be postcrosslinked, the crosslinkable resin molded article of the present invention can sufficiently exhibit the desired effect.
本発明の架橋性樹脂成形体は、塊状重合を完結させて得られるものであり、保管中にさらに重合反応が進行するという恐れがない。また、本発明の架橋性樹脂成形体は、ラジカル発生剤などの架橋剤を含有してなるが、架橋反応を起す温度以上に加熱しない限り、表面硬度が変化するなどの不具合を生じず、保存安定性に優れる。
本発明の架橋性樹脂成形体は、例えば、プリプレグとして、本発明の架橋樹脂成形体及
び積層体の製造に好適に用いられる。
The crosslinkable resin molded article of the present invention is obtained by completing bulk polymerization, and there is no fear that the polymerization reaction further proceeds during storage. In addition, the crosslinkable resin molded article of the present invention contains a crosslinking agent such as a radical generator, but does not cause a problem such as a change in surface hardness unless it is heated to a temperature at which a crosslinking reaction is caused or not. Excellent stability.
The crosslinkable resin molded article of the present invention is suitably used for the production of the crosslinked resin molded article and laminate of the present invention, for example, as a prepreg.
(架橋樹脂成形体)
本発明の架橋樹脂成形体は、本発明の重合性組成物を塊状重合し、得られた重合体を架橋してなるものである。かかる架橋樹脂成形体は、例えば、前記架橋性樹脂成形体を架橋することにより得られる。本発明の架橋樹脂成形体においては、前記一官能化合物、二官能化合物、及び三官能化合物が基材樹脂に結合し、実質的に遊離の状態で存在するものがなく、例えば、一官能化合物が揮発成分となることがない。めっき対象物に揮発成分が多い場合、めっき形成及び対象物への付着を阻害ことから、該対象物のめっき性が低下する。本発明の架橋樹脂成形体には、前記の通り、揮発成分が実質的に含まれないため、該成形体は優れためっき性を有する。本発明の架橋樹脂成形体の揮発成分量としては、該成形体中、通常、0.1重量%未満である。本発明の架橋樹脂成形体を用いてなる積層体においても同様に揮発成分量は、通常、0.1重量%未満であり、当該成分は実質的に含まれないため、本発明の積層体は優れためっき性を有する。
(Crosslinked resin molding)
The crosslinked resin molded product of the present invention is obtained by bulk polymerizing the polymerizable composition of the present invention and crosslinking the resulting polymer. Such a crosslinked resin molded body can be obtained, for example, by crosslinking the crosslinkable resin molded body. In the crosslinked resin molded article of the present invention, there is no monofunctional compound, bifunctional compound, and trifunctional compound that are bonded to the base resin and exist in a substantially free state. It does not become a volatile component. When there are many volatile components in a plating target object, since plating formation and adhesion to a target object are inhibited, the plating property of this target object falls. As mentioned above, since the volatile component is not substantially contained in the crosslinked resin molded body of the present invention, the molded body has excellent plating properties. The amount of volatile components of the crosslinked resin molded product of the present invention is usually less than 0.1% by weight in the molded product. Similarly, in the laminated body using the crosslinked resin molded body of the present invention, the amount of volatile components is usually less than 0.1% by weight and the component is not substantially contained. Excellent plating properties.
架橋性樹脂成形体の架橋は、該成形体を、該成形体を構成する重合体において架橋反応が生ずる温度以上に維持することにより行うことができる。加熱温度は、通常、架橋剤により架橋反応が誘起される温度以上である。例えば、架橋剤としてラジカル発生剤を使用する場合、通常、1分間半減期温度以上、好ましくは1分間半減期温度より5℃以上高い温度、より好ましくは1分間半減期温度より10℃以上高い温度である。典型的には、100〜300℃、好ましくは150〜250℃の範囲である。加熱時間は、0.1〜180分間、好ましくは0.5〜120分間、より好ましくは1〜60分間の範囲である。また、本発明の重合性組成物を、前記架橋性樹脂成形体が架橋する温度以上に維持することにより、具体的には、ここに記載する、温度及び時間で加熱することにより、シクロオレフィンモノマーの塊状重合と、当該重合により生ずるシクロオレフィンポリマーにおける架橋反応とを共に進行させて、本発明の架橋樹脂成形体を製造することも可能である。このようにして架橋樹脂成形体を製造する場合、前記(a)の方法に準じ、例えば、支持体として銅箔を用いれば、銅張積層板〔Copper Clad Laminates (CCL)〕を得ることができる。 Crosslinking of the crosslinkable resin molded body can be performed by maintaining the molded body at a temperature equal to or higher than a temperature at which a crosslinking reaction occurs in the polymer constituting the molded body. The heating temperature is usually equal to or higher than the temperature at which a crosslinking reaction is induced by the crosslinking agent. For example, when a radical generator is used as a crosslinking agent, it is usually at least 1 minute half-life temperature, preferably at least 5 ° C. above 1-minute half-life temperature, more preferably at least 10 ° C. above 1-minute half-life temperature. It is. Typically, it is in the range of 100 to 300 ° C, preferably 150 to 250 ° C. The heating time is in the range of 0.1 to 180 minutes, preferably 0.5 to 120 minutes, more preferably 1 to 60 minutes. Further, by maintaining the polymerizable composition of the present invention at a temperature equal to or higher than the temperature at which the crosslinkable resin molded article is crosslinked, specifically, by heating at the temperature and time described herein, the cycloolefin monomer It is also possible to produce the crosslinked resin molded article of the present invention by proceeding together with the bulk polymerization of the polymer and the crosslinking reaction in the cycloolefin polymer produced by the polymerization. In the case of producing a crosslinked resin molded body in this way, a copper clad laminate (Copper Clad Laminates (CCL)) can be obtained in accordance with the method (a), for example, by using a copper foil as a support. .
(積層体)
本発明の積層体は、少なくとも、前記架橋性樹脂成形体、又は前記架橋樹脂成形体からなる層を有してなるものである。架橋性樹脂成形体、又は架橋樹脂成形体からなる層が複数存在する場合、両成形体はそれぞれ、連続的に積層されていても、他の層を挟んで間接的に積層されていてもよい。
本発明の架橋性樹脂成形体からなる層を有する積層体としては、例えば、前記(a)の方法で得られる、銅箔と架橋性樹脂成形体とが層状に一体化してなるRCCが挙げられる。また、本発明の架橋樹脂成形体からなる層を有する積層体としては、例えば、前記(a)の方法に準じて得られる、銅箔と架橋樹脂成形体とが層状に一体化してなるCCLが挙げられる。前記(a)の方法において、支持体として、別途得られた架橋樹脂成形体を用いれば、架橋性樹脂成形体からなる層と架橋樹脂成形体からなる層とを有する積層体を得ることもできる。
また、架橋性樹脂成形体がシート状又はフィルム状である場合、該成形体、及び所望により、シート状又はフィルム状の架橋樹脂成形体を、任意に積層し、又はさらに、例えば、前記金属箔を積層し、熱プレスして架橋することにより、架橋樹脂成形体からなる層を有する、本発明の積層体が得られる。その際、前記RCCやCCLなどの積層体を積層してもよい。熱プレスするときの圧力は、通常、0.5〜20MPa、好ましくは3〜10MPaである。熱プレスは、真空又は減圧雰囲気下で行ってもよい。熱プレスは、平板成形用のプレス枠型を有する公知のプレス機、シートモールドコンパウンド(SMC)やバルクモールドコンパウンド(BMC)などのプレス成形機を用いて行なうことができる。
(Laminate)
The laminate of the present invention comprises at least the crosslinkable resin molded body or a layer made of the crosslinked resin molded body. When there are a plurality of layers formed of a crosslinkable resin molded product or a crosslinked resin molded product, both molded products may be laminated continuously or indirectly with another layer interposed therebetween. .
As a laminated body which has a layer which consists of a crosslinkable resin molding of this invention, RCC obtained by the method of said (a) and which integrates copper foil and a crosslinkable resin molding in a layer form is mentioned, for example. . Moreover, as a laminated body which has a layer which consists of a crosslinked-resin molded object of this invention, CCL obtained by conforming to the method of said (a), and the copper foil and the crosslinked-resin molded object integrated in layered form, for example. Can be mentioned. In the method (a), if a separately obtained cross-linked resin molded body is used as the support, a laminate having a layer made of a cross-linkable resin molded body and a layer made of the cross-linked resin molded body can be obtained. .
Further, when the crosslinkable resin molded body is in the form of a sheet or film, the molded body and, optionally, the sheet-shaped or film-shaped crosslinked resin molded body is arbitrarily laminated, or further, for example, the metal foil Are laminated and hot-pressed for crosslinking to obtain a laminate of the present invention having a layer composed of a crosslinked resin molded article. In that case, you may laminate | stack laminated bodies, such as said RCC and CCL. The pressure at the time of hot pressing is usually 0.5 to 20 MPa, preferably 3 to 10 MPa. The hot pressing may be performed in a vacuum or a reduced pressure atmosphere. The hot pressing can be performed using a known press having a press frame mold for flat plate forming, a press molding machine such as a sheet mold compound (SMC) or a bulk mold compound (BMC).
本発明の積層体は、低誘電率及び低誘電正接といった、シクロオレフィンポリマーに特有の優れた電気的特性を有しており、高周波領域での伝送ロスが少なく、かつ配線埋め込み性、耐熱性、及びめっき性に優れるため、広範囲の用途を有する高周波基板材料として好適に用いることができる。 The laminate of the present invention has excellent electrical characteristics unique to cycloolefin polymers, such as low dielectric constant and low dielectric loss tangent, has low transmission loss in a high frequency region, and has wiring embedding properties, heat resistance, Moreover, since it is excellent in plating properties, it can be suitably used as a high-frequency substrate material having a wide range of uses.
以下、実施例及び比較例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例及び比較例における部及び%は、特に断りのない限り重量基準である。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. In addition, the part and% in an Example and a comparative example are a basis of weight unless there is particular notice.
実施例及び比較例における各特性は、以下の方法に従い測定し、評価した。
(1)揮発成分量
積層体をエッチングして銅箔を除去した後、1mm角程度に裁断後、そのサンプルをちょうど1gになるよう定量した。得られた裁断後のサンプルをトルエンに2時間浸漬し、トルエンに溶解した揮発成分をガスクロマトグラフィー(島津製作所社製、型番GC−2010)により定量し、以下の基準に従って評価した。
〔評価基準〕
○:揮発成分0.1%未満
×:揮発成分0.1%以上
(2)めっき性
積層体上に、L/S=30μmで配線長50mmの50本の配線パターンを形成し、目視観察により、以下の基準に従って評価した。
〔評価基準〕
○:50本の配線のいずれもが形状に乱れが無い
△:一部形状に乱れはあるが、配線の欠損は無い
×:配線に欠損がある
(3)誘電正接
積層体を3cm角に切り出し、エッチングして銅箔を除去した後、インピーダンスアナライザー(アジレントテクノロジー社製、型番E4991A)を用いて20℃で周波数1GHzにおける誘電正接(tanδ)を容量法にて測定し、以下の基準で評価した。
〔評価基準〕
○:0.002以下
×:0.002超
(4)配線埋め込み性
プリプレグを回路基板(L/S=30μmの配線を15本配置した試験基板)上に重ね、200℃で10分間、3MPaにて加熱プレスを行い積層体を得た。該積層体を、配線方向に対し垂直な方向で任意に3箇所で切断した。得られた積層体の切断面を目視により観察し、回路基板上の樹脂層への配線埋め込み性について以下の基準で評価した。なお、○及び◎の評価であれば、積層体は高周波基板材料として問題なく機能する。
〔評価基準〕
◎:配線が埋め込まれていない部分がない
○:配線が一部埋め込まれていない
×:配線が埋め込まれていない
(5)耐熱性
積層体をエッチングして銅箔を除去した後、TMA(SIIナノテクノロジー社製、SS6100標準型)を用いてガラス転移点(Tg)を測定し、以下の基準で耐熱性を評価
した。
〔評価基準〕
○:160℃超
×:160℃以下
(6)難燃性
積層体の銅箔をエッチング処理により取り除いたものから短冊状試験片(15mm×125mm)を切り出し、炎を該試験片に10秒間接炎し、離炎後の有炎を観察し、以下の
基準で評価した。
○ : 離炎後の有炎はあるが、間もなく消える
× : 離炎後の有炎が上部まで達し、激しく燃えた
Each characteristic in an Example and a comparative example was measured and evaluated according to the following methods.
(1) Volatile component amount After removing the copper foil by etching the laminate, the sample was cut to about 1 mm square, and the sample was quantified to be exactly 1 g. The obtained sample after cutting was immersed in toluene for 2 hours, and volatile components dissolved in toluene were quantified by gas chromatography (manufactured by Shimadzu Corporation, model number GC-2010), and evaluated according to the following criteria.
〔Evaluation criteria〕
○: Volatile component less than 0.1% ×: Volatile component 0.1% or more (2) Plating property On the laminate, 50 wiring patterns of L / S = 30 μm and a wiring length of 50 mm were formed and visually observed. Evaluation was made according to the following criteria.
〔Evaluation criteria〕
○: All of the 50 wirings have no shape irregularity. Δ: Some shapes are disordered, but there is no wiring defect. ×: There is a wiring defect. (3) Dielectric loss tangent The laminate is cut into 3 cm square. After removing the copper foil by etching, the dielectric loss tangent (tan δ) at a frequency of 1 GHz was measured at 20 ° C. using an impedance analyzer (manufactured by Agilent Technologies, model number E4991A), and evaluated according to the following criteria: .
〔Evaluation criteria〕
○: 0.002 or less x: More than 0.002 (4) Wiring embedding property A prepreg is stacked on a circuit board (a test board on which 15 wires of L / S = 30 μm are arranged), and is set to 3 MPa at 200 ° C. for 10 minutes. Then, a heat press was performed to obtain a laminate. The laminate was arbitrarily cut at three points in a direction perpendicular to the wiring direction. The cut surface of the obtained laminate was visually observed, and the wiring embeddability into the resin layer on the circuit board was evaluated according to the following criteria. In addition, if it is evaluation of (circle) and (double-circle), a laminated body will function without a problem as a high frequency board material.
〔Evaluation criteria〕
A: There is no portion where the wiring is not embedded. ○: A portion of the wiring is not embedded. X: The wiring is not embedded. (5) Heat resistance After removing the copper foil by etching the laminate, TMA (SII The glass transition point (Tg) was measured using a nanotechnology company, SS6100 standard type, and the heat resistance was evaluated according to the following criteria.
〔Evaluation criteria〕
○: Over 160 ° C. x: 160 ° C. or less (6) Flame retardance A strip-shaped test piece (15 mm × 125 mm) is cut out from the copper foil of the laminate removed by etching, and the flame is indirectly applied to the test piece for 10 seconds. Flames were observed and the flames after the flare off were observed and evaluated according to the following criteria.
○: Although there is a flaming after the flare off, it will disappear soon. ×: The flaming after the flare has reached the top and burned violently.
実施例1
ベンジリデン(1、3−ジメシチル−4−イミダゾリジン−2−イリデン)(トリシクロヘキシルホスフィン)ルテニウムジクロリド 0.05部と、トリフェニルホスフィン 0.01部とを、インデン 1.51部に溶解させて触媒液を調製した。
これとは別に、シクロオレフィンモノマーとして、エチリデンテトラシクロ[6.2.1.13,6.02,7]ドデカ−4−エン(ETD)60部、ジシクロペンタジエン(DCPD)40部;連鎖移動剤としてジビニルベンゼン 1.6部;架橋剤としてジ−t−ブチルパーオキサイド(1分間半減期温度186℃)1.14部;一官能化合物としてベンジルメタクリレート 12部、二官能化合物としてトリシクロデカンジメタノールジメタクリレート 5部、及び三官能化合物としてトリメチロールプロパントリメタクリレート 20部;充填剤として、シリカ(アドマテックス社製、製品名SO−E2、シランカップリング剤処理品 平均粒径0.5μm)100部と、非ハロゲン難燃剤である三酸化アンチモン(PATOX−M、日本精鉱社製)20部、及びハロゲン難燃剤であるエタン−1、2−ビス(ペンタブロモフェニル)(SAYTEX8010、アルベマール社製)40部;並びにフェノール系老化防止剤として3,5−ジ−t−ブチル−4−ヒドロキシアニソール0.28部を混合してモノマー液を調製した。これに上記触媒液をシクロオレフィンモノマー100g当り0.62mLの割合で加えて撹拌し、重合性組成物を調製した。
ついで、得られた重合性組成物をガラスクロス(Eガラス)に含浸させ、これを120℃
にて3.5分間で塊状重合反応を行い、厚さ0.13mmのプリプレグを得た。
次に、作製したプリプレグ6枚を積層し、次いで12μmF0銅箔(シランカップリン
グ剤処理電解銅箔、古河電工社製)で挟み、180℃、60分間、3MPaにて加熱プレスを行って積層体を得た。得られた積層体について、揮発成分量、誘電正接、耐熱性、及び難燃性を評価した。一方、配線埋め込み性は、前記(4)配線埋め込み性に記載した方法により別途積層体を得、それを用いて評価した。それらの結果を表1に示す。なお、揮発成分量は0%であった。
次いで、めっき前処理として、上記水洗後の積層体を、アルカップアクチべータMAT−1−A(上村工業社製)が200mL/L、アルカップアクチべータM AT−1−B(上村工業社製)が30mL/L、及び水酸化ナトリウムが0.35g/Lになるように調整した60℃のPd塩含有めっき触媒水溶液に5分間浸漬した。この積層体を水槽に1分間揺動浸漬し、更に別の水槽に1分間揺動浸漬することにより水洗した。次いで、アルカップレデューサーMAB−4−A(上村工業社製)が20mL/L、及びアルカップレデューサーMAB−4−B(上村工業社製)が200mL/Lになるように調整した溶液に35℃で、3分間浸漬し、めっき触媒を還元処理した。このようにしてめっき触媒を吸着させ、めっき前処理を施した積層体を得た。
Example 1
Benzylidene (1,3-dimesityl-4-imidazolidin-2-ylidene) (tricyclohexylphosphine) ruthenium dichloride 0.05 part and triphenylphosphine 0.01 part are dissolved in indene 1.51 part to form a catalyst. A liquid was prepared.
Apart from this, as cycloolefin monomer, ethylidenetetracyclo [6.2.1.1 3,6 . 0 2,7 ] 60 parts dodec-4-ene (ETD), 40 parts dicyclopentadiene (DCPD); 1.6 parts divinylbenzene as a chain transfer agent; di-tert-butyl peroxide (half a minute for 1 minute) (Initial temperature 186 ° C.) 1.14 parts; 12 parts benzyl methacrylate as monofunctional compound, 5 parts tricyclodecane dimethanol dimethacrylate as bifunctional compound, and 20 parts trimethylolpropane trimethacrylate as trifunctional compound; 100 parts of silica (manufactured by Admatechs, product name SO-E2, silane coupling agent treated average particle size 0.5 μm) and antimony trioxide which is a non-halogen flame retardant (PATOX-M, manufactured by Nippon Seiko Co., Ltd.) 20 parts, and ethane-1,2-bis (pentabromophenyl) (SAY), which is a halogen flame retardant EX8010, manufactured by Albemarle) 40 parts; was prepared and phenolic antioxidant as 3,5-di -t- butyl-4-hydroxyanisole 0.28 parts were mixed with the monomer solution. The above catalyst solution was added thereto at a rate of 0.62 mL per 100 g of cycloolefin monomer and stirred to prepare a polymerizable composition.
The resulting polymerizable composition was then impregnated into glass cloth (E glass),
The bulk polymerization reaction was performed in 3.5 minutes to obtain a prepreg having a thickness of 0.13 mm.
Next, 6 sheets of the prepared prepregs were laminated, then sandwiched between 12 μm F0 copper foil (silane coupling agent-treated electrolytic copper foil, manufactured by Furukawa Electric Co., Ltd.), and heated and pressed at 180 ° C. for 60 minutes at 3 MPa to obtain a laminate. Got. About the obtained laminated body, the amount of volatile components, dielectric loss tangent, heat resistance, and flame retardance were evaluated. On the other hand, the wiring embedding property was evaluated by separately obtaining a laminate by the method described in the above (4) Wiring embedding property. The results are shown in Table 1. The amount of volatile components was 0%.
Next, as a pretreatment for plating, the above-mentioned water-washed laminate is 200 mL / L of Alcup Activator MAT-1-A (manufactured by Uemura Kogyo Co., Ltd.), Alcup Activator MAT-1-B ( (Made by Uemura Kogyo Co., Ltd.) was immersed in a 60 ° C. Pd salt-containing plating catalyst aqueous solution adjusted to 30 mL / L and sodium hydroxide to 0.35 g / L for 5 minutes. This laminate was immersed in a water tank for 1 minute, and further washed in water by immersion in another water tank for 1 minute. Next, the solution was adjusted to 35 ° C. so that Alcap Reducer MAB-4-A (Uemura Kogyo) was 20 mL / L and Alcup Reducer MAB-4-B (Uemura Kogyo) was 200 mL / L. And dipping for 3 minutes to reduce the plating catalyst. In this way, a plating catalyst was adsorbed to obtain a laminate subjected to pretreatment for plating.
次いで、めっき前処理後の積層体を、スルカップPSY−1A(上村工業社製)100mL/L、スルカップPSY−1B(上村工業社製)40mL/L、及びホルマリン0.2モル/Lとなるように調整した水溶液に空気を吹き込みながら、温度36℃、5分間浸漬して無電解銅めっき処理を行い積層体上に金属薄膜層を形成した。無電解めっき処理により金属薄膜層が形成された積層体を、更に水槽に1分間揺動浸漬し、更に別の水槽に1 分間揺動浸漬することにより水洗し、乾燥し、防錆処理を施し、無電解めっき皮膜が形成された多層回路基板を得た。 Next, the laminate after the plating pretreatment is 100 mL / L of Sulcup PSY-1A (manufactured by Uemura Kogyo Co., Ltd.), 40 mL / L of Sulcup PSY-1B (manufactured by Uemura Kogyo Co., Ltd.), and 0.2 mol / L of formalin. While blowing air into the prepared aqueous solution, the film was immersed for 5 minutes at a temperature of 36 ° C. to perform an electroless copper plating process to form a metal thin film layer on the laminate. The laminate on which the metal thin film layer is formed by electroless plating is further immersed in a water tank for 1 minute, and further immersed in another water tank for 1 minute, washed with water, dried, and subjected to rust prevention treatment. A multilayer circuit board on which an electroless plating film was formed was obtained.
この防錆処理が施された多層回路基板表面に、市販の感光性レジストのドライフィルムを熱圧着して貼り付け、さらに、このドライフィルム上に密着性評価用パターンに対応するパターンのマスクを密着させ露光し、次いで現像してレジストパターンを得た。次に硫酸100g/Lの水溶液に25℃で1分間浸漬させ防錆剤を除去し、レジスト非形成部分に電解銅めっきを施し厚さ18μmの電解銅めっき膜を形成させた。次いで、レジストパターンを剥離液にて剥離除去し、塩化第二銅と塩酸の混合水溶液によりエッチング処理を行うことにより、前記金属薄膜および電解銅めっき膜からなる配線パターンを形成し両面2層の配線パターン付き多層回路基板aを得、最後に、170℃で30分間アニール処理を行った。得られた多層回路基板aについてめっき性の評価を行った。評価結果を表1に示す。 A dry film of a commercially available photosensitive resist is attached to the surface of the multilayer circuit board that has been subjected to the antirust treatment by thermocompression bonding, and a mask having a pattern corresponding to the adhesion evaluation pattern is adhered to the dry film. The resist pattern was obtained by exposing to light and then developing. Next, it was immersed in an aqueous solution of 100 g / L of sulfuric acid at 25 ° C. for 1 minute to remove the rust preventive, and electrolytic copper plating was applied to the resist non-formed portion to form an electrolytic copper plating film having a thickness of 18 μm. Next, the resist pattern is stripped and removed with a stripping solution, and an etching process is performed with a mixed aqueous solution of cupric chloride and hydrochloric acid to form a wiring pattern composed of the metal thin film and the electrolytic copper plating film. A patterned multilayer circuit board a was obtained, and finally an annealing treatment was performed at 170 ° C. for 30 minutes. The obtained multilayer circuit board a was evaluated for plating properties. The evaluation results are shown in Table 1.
比較例1
トリシクロデカンジメタノールジメタクリレートの配合量を0部にしたこと以外は実施例1と同様にしてプリプレグ、積層体、及び多層回路基板を得、同様に評価した。結果を表1に示す。なお、揮発成分量は0.5%以上であった。
Comparative Example 1
A prepreg, a laminate, and a multilayer circuit board were obtained and evaluated in the same manner as in Example 1 except that the amount of tricyclodecane dimethanol dimethacrylate was changed to 0 part. The results are shown in Table 1. The volatile component amount was 0.5% or more.
比較例2
ベンジルメタクリレートの配合量を0部にしたこと以外は実施例1と同様にしてプリプレグ、積層体、及び多層回路基板を得、同様に評価した。結果を表1に示す。なお、揮発成分量は0%であった。
Comparative Example 2
A prepreg, a laminate, and a multilayer circuit board were obtained and evaluated in the same manner as in Example 1 except that the amount of benzyl methacrylate was 0 part. The results are shown in Table 1. The amount of volatile components was 0%.
比較例3
トリメチロールプロパントリメタクリレートの配合量を0部にしたこと以外は実施例1と同様にしてプリプレグ、積層体、及び多層回路基板を得、同様に評価した。結果を表1に示す。なお、揮発成分量は0.5%以上であった。
Comparative Example 3
A prepreg, a laminate, and a multilayer circuit board were obtained and evaluated in the same manner as in Example 1 except that the amount of trimethylolpropane trimethacrylate was changed to 0 part. The results are shown in Table 1. The volatile component amount was 0.5% or more.
表1より、実施例1で得られた積層体は、硬化後に揮発成分が残存せず、めっき性、誘電正接、配線埋め込み性、耐熱性、及び難燃性が非常に優れることがわかる。一方、二官能メタクリレートを含有しない重合性組成物を用いて得られた比較例1の積層体では、硬化後に揮発成分が残存し、めっき性、誘電正接、流動性、耐熱性、及び難燃性が劣り、一官能メタクリレートを含有しない重合性組成物を用いて得られた比較例2の積層体は、硬化後の揮発成分が残存せず、めっき性、誘電正接、耐熱性、及び難燃性は実施例1のものと同等であるが、配線埋め込み性に劣り、三官能メタクリレートを含有しない重合性組成物を用いて得られた比較例3の積層体では、硬化後に揮発成分が残存し、めっき性、誘電正接、配線埋め込み性、耐熱性、及び難燃性が劣ることが分かる。 From Table 1, it can be seen that the laminate obtained in Example 1 has no volatile components remaining after curing, and is extremely excellent in plating property, dielectric loss tangent, wiring embedding property, heat resistance, and flame retardancy. On the other hand, in the laminate of Comparative Example 1 obtained using a polymerizable composition containing no bifunctional methacrylate, volatile components remain after curing, plating properties, dielectric loss tangent, fluidity, heat resistance, and flame retardancy. The laminate of Comparative Example 2 obtained by using a polymerizable composition that is inferior and does not contain a monofunctional methacrylate has no volatile component after curing, plating properties, dielectric loss tangent, heat resistance, and flame retardancy Is equivalent to that of Example 1, but inferior in wiring embedding, and in the laminate of Comparative Example 3 obtained using a polymerizable composition not containing trifunctional methacrylate, volatile components remain after curing, It can be seen that the plating property, dielectric loss tangent, wiring embedding property, heat resistance, and flame retardancy are inferior.
Claims (7)
A cycloolefin monomer, a polymerization catalyst, a crosslinking agent, a monofunctional compound having one vinylidene group, a bifunctional compound having two vinylidene groups, a trifunctional compound having three vinylidene groups, and a filler, And the content ratio of the monofunctional compound, the bifunctional compound, and the trifunctional compound is 1 to 20: 0.1 to 20:10 to 25 in a weight ratio (monofunctional compound: bifunctional compound: trifunctional compound). A polymerizable composition, characterized in that the amount of volatile components of a crosslinked resin molded body obtained by bulk polymerization and cross-linking this is less than 0.1% by weight. .
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